Aromatic amine derivative and organic electroluminescent devices containing the same

ABSTRACT

Disclosed are an aromatic amine derivative and an organic electroluminescent device including the same. A fluorenyl/silafluorenyl group having an ortho-substituted group is introduced into the structure of the aromatic amine derivative. The aromatic amine derivative may be used as a light-emitting material in a light-emitting layer of an organic electroluminescent device. These novel compounds can provide better device performance.

CROSS-REFERENCE TO RELATED APPLICATION(S)

The present disclosure claims priority to a Chinese patent application No. CN 201910788747.0 filed on Aug. 26, 2019, disclosure of which is incorporated herein by reference in its entirety.

TECHNICAL FIELD

The present disclosure relates to aromatic amine derivative compounds for organic electronic devices, for example, organic light-emitting devices. More particularly, the present disclosure relates to an aromatic amine derivative compound, and an organic electroluminescent device and a compound formulation including the compound.

BACKGROUND

Organic electronic devices include, but are not limited to, the following types: organic light-emitting diodes (OLEDs), organic field-effect transistors (O-FETs), organic light-emitting transistors (OLETs), organic photovoltaic devices (OPVs), dye-sensitized solar cells (DSSCs), organic optical detectors, organic photoreceptors, organic field-quench devices (OFQDs), light-emitting electrochemical cells (LECs), organic laser diodes and organic plasmon emitting devices.

In 1987, Tang and Van Slyke of Eastman Kodak reported a bilayer organic electroluminescent device, which comprises an arylamine hole transporting layer and a tris-8-hydroxyquinolato-aluminum layer as the electron and emitting layer (Applied Physics Letters, 1987, 51 (12): 913-915). Once a bias is applied to the device, green light was emitted from the device. This device laid the foundation for the development of modern organic light-emitting diodes (OLEDs). State-of-the-art OLEDs may comprise multiple layers such as charge injection and transporting layers, charge and exciton blocking layers, and one or multiple emissive layers between the cathode and anode. Since the OLED is a self-emitting solid state device, it offers tremendous potential for display and lighting applications. In addition, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications such as fabrication on flexible substrates.

The OLED can be categorized as three different types according to its emitting mechanism. The OLED invented by Tang and van Slyke is a fluorescent OLED. It only utilizes singlet emission. The triplets generated in the device are wasted through nonradiative decay channels. Therefore, the internal quantum efficiency (IQE) of the fluorescent OLED is only 25%. This limitation hindered the commercialization of OLED. In 1997, Forrest and Thompson reported phosphorescent OLED, which uses triplet emission from heavy metal containing complexes as the emitter. As a result, both singlet and triplets can be harvested, achieving 100% IQE. The discovery and development of phosphorescent OLED contributed directly to the commercialization of active-matrix OLED (AMOLED) due to its high efficiency. Recently, Adachi achieved high efficiency through thermally activated delayed fluorescence (TADF) of organic compounds. These emitters have small singlet-triplet gap that makes the transition from triplet back to singlet possible. In the TADF device, the triplet excitons can go through reverse intersystem crossing to generate singlet excitons, resulting in high IQE.

The emitting color of the OLED can be achieved by emitter structural design. An OLED may comprise one emitting layer or a plurality of emitting layers to achieve desired spectrum. In the case of green, yellow, and red OLEDs, phosphorescent emitters have successfully reached commercialization. Blue phosphorescent device still suffers from non-saturated blue color, short device lifetime, and high operating voltage. Commercial full-color OLED displays normally adopt a hybrid strategy, using fluorescent blue and phosphorescent yellow, or red and green.

Although fluorescent blue OLEDs have longer lifetimes than phosphorescent blue OLEDs, the lifetime and the efficiency of fluorescent blue OLEDs need to be further improved to meet the increasing requirements in the display field. Therefore, it is a very important project to improve the lifetime and the efficiency of fluorescent blue devices.

CN108558678A disclosed a compound having a structure represented by the following general formula:

wherein at least one of Ar₁ to Ar₄ is selected from a naphthyl substituent having the following structures:

Specific examples include

etc. Compounds disclosed in this application have to include a naphthalene ring structure, and the inventors focus on the use of 1-naphthalene and 2-naphthalene substituents in pyrene-based triarylamine compounds rather than the use of fluorene/silafluorene structures with ortho-substituents. This application has neither disclosed or instructed the use of aryl/heteroaryl groups other than naphthalene in triarylamine compounds based on pyrene or other aryl/heteroaryl groups, nor noticed the special advantages of fluorene/silafluorene structures with ortho-substituents.

US20150255736A disclosed a pyrene-based triarylamine compound substituted with silafluorene:

wherein at least one of Ar₁ to Ar₄ has a structure represented by the following general formula:

Specific examples include

This application has disclosed the introduction of a silafluorene structure into pyrene-based triarylamine compounds, but not noticed the special advantages of fluorene/silafluorene structures with ortho-substituents.

TW201925161A disclosed a compound represented by the following general formula:

wherein Ar⁴ has a structure represented by the general formula:

wherein G is a central segment of a fluorescent material such as pyrene, chrysene, and anthracene, n is 0 or 1, r is 0 to 2, s and p each have a range from 0 to 10, and m and q each have a range from 1 to 10.

Specific examples disclosed include

This application relates to the study of blue materials having a fluorene ring-based triarylamine structure. However, in structures disclosed in this application, two or more structural units of fluorene rings have to be included in a single Ar group. Moreover, OLED devices are prepared by a solution method in this application, and multiple fluorene ring structures and long alkyl chains in the disclosed compounds are all favorable to the use of the solution method for preparing devices. Meanwhile, due to the introduction of multiple structural units of fluorene rings and the long alkyl chains, the compounds disclosed in this application are not favorable to the use of a vacuum evaporation method for preparing OLED devices. Therefore, this application has neither disclosed or instructed the inclusion of only one structural unit of fluorene ring in a single Ar group nor noticed the special advantages of fluorene/silafluorene structures with ortho-substituents.

These documents have disclosed a large number of fluorescent light-emitting materials with an aromatic amine structure with a pyrene core. However, the fluorescent light-emitting materials still need to be further developed to obtain higher device efficiency, a longer device lifetime, and bluer light emission. After in-depth researches, the inventor has found that novel aromatic amine derivative compounds obtained through the introduction of a fluorenyl/silafluorenyl group with ortho-substituted groups into the aromatic amine structure of this kind of material can provide better device performance when used as light-emitting materials in organic light-emitting devices.

SUMMARY

The present disclosure aims to provide a series of novel compounds having an aromatic amine structure to solve at least part of the above-mentioned problems. These compounds may be used as light-emitting materials in organic electroluminescent devices. These novel compounds can provide better device performance

According to an embodiment of the present disclosure, disclosed is a compound having a structure of Formula 1:

-   -   in Formula 1,     -   A is substituted or unsubstituted aryl having 10 to 60 ring         atoms or substituted or unsubstituted heteroaryl having 10 to 60         ring atoms;     -   n is an integer greater than or equal to 1, m is an integer         greater than or equal to 0, and n+m is greater than or equal to         2; when n is greater than or equal to 2, B may be the same or         different structures; when m is greater than or equal to 2, E         may be the same or different structures;     -   E has a structure represented by Formula 2:

-   -   in Formula 2, * represents a position where E is joined to A;     -   wherein Ar and Ar₁ are each independently selected from the         group consisting of: substituted or unsubstituted aryl having 6         to 30 ring carbon atoms and substituted or unsubstituted         heteroaryl having 3 to 30 ring atoms;     -   B has a structure represented by Formula 3:

-   -   in Formula 3, * represents a position where B is joined to A;     -   wherein R is selected from the group consisting of: substituted         or unsubstituted aryl having 6 to 30 ring carbon atoms and         substituted or unsubstituted heteroaryl having 3 to 30 ring         atoms; and when R is selected from aryl, R is not substituted or         unsubstituted naphthyl;     -   wherein Ar₂ has a structure represented by Formula 4:

-   -   and Ar₂ includes only one fluorene ring structure, azafluorene         ring structure, spirobifluorene ring structure, or         azaspirobifluorene ring structure;     -   in Formula 4, * represents a position where Ar₂ is joined to N         shown in Formula 3;     -   X is C or Si;     -   L is selected from a single bond, substituted or unsubstituted         arylene having 6 to 60 carbon atoms, or substituted or         unsubstituted heteroarylene having 3 to 60 carbon atoms;     -   X₁ to X₈ are each independently selected from C, CR′ or N, and         two adjacent C are present in X₁ to X₄, wherein one of the two         adjacent C is joined to L, and the other one of the two adjacent         C is joined to R″;     -   wherein R_(a), R_(b), and R′ are each independently selected         from the group consisting of: hydrogen, deuterium, halogen,         substituted or unsubstituted alkyl having 1 to 20 carbon atoms,         substituted or unsubstituted cycloalkyl having 3 to 20 ring         carbon atoms, substituted or unsubstituted heteroalkyl having 1         to 20 carbon atoms, substituted or unsubstituted arylalkyl         having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy         having 1 to 20 carbon atoms, substituted or unsubstituted         aryloxy having 6 to 30 carbon atoms, substituted or         unsubstituted alkenyl having 2 to 20 carbon atoms, substituted         or unsubstituted aryl having 6 to 30 carbon atoms, substituted         or unsubstituted heteroaryl having 3 to 30 carbon atoms,         substituted or unsubstituted alkylsilyl having 3 to 20 carbon         atoms, substituted or unsubstituted arylsilyl having 6 to 20         carbon atoms, substituted or unsubstituted amino having 0 to 20         carbon atoms, an acyl group, a carbonyl group, a carboxylic acid         group, an ester group, a nitrile group, an isonitrile group, a         thiol group, a sulfinyl group, a sulfonyl group, a phosphino         group, and combinations thereof;     -   wherein R″ is each independently selected from the group         consisting of: deuterium, halogen, substituted or unsubstituted         alkyl having 1 to 20 carbon atoms, substituted or unsubstituted         cycloalkyl having 3 to 20 ring carbon atoms, substituted or         unsubstituted heteroalkyl having 1 to 20 carbon atoms,         substituted or unsubstituted arylalkyl having 7 to 30 carbon         atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon         atoms, substituted or unsubstituted aryloxy having 6 to 30         carbon atoms, substituted or unsubstituted alkenyl having 2 to         20 carbon atoms, substituted or unsubstituted aryl having 6 to         30 carbon atoms, substituted or unsubstituted heteroaryl having         3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl         having 3 to 20 carbon atoms, substituted or unsubstituted         arylsilyl having 6 to 20 carbon atoms, substituted or         unsubstituted amino having 0 to 20 carbon atoms, an acyl group,         a carbonyl group, a carboxylic acid group, an ester group, a         nitrile group, an isonitrile group, a thiol group, a sulfinyl         group, a sulfonyl group, a phosphino group, and combinations         thereof; and     -   wherein in Formula 4, substituents R_(a) and R_(b) can be         optionally joined to form a ring, and two adjacent substituents         R′ can be optionally joined to form a ring.

According to another embodiment of the present disclosure, further disclosed is an electroluminescent device, including an anode, a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer includes the compound having a structure represented by Formula 1. The specific structure of the compound is shown above.

According to another embodiment of the present disclosure, further disclosed is a compound formulation including the compound having a structure represented by Formula 1. The specific structure of the compound is shown above.

The novel pyrene compounds having an aromatic amine structure disclosed by the present disclosure may be used as light-emitting materials in electroluminescent devices. These novel compounds can provide better device performance, such as higher efficiency, bluer light emission, and a longer lifetime.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a schematic diagram of an organic light-emitting apparatus that may include a compound and a compound formulation disclosed by the present disclosure.

FIG. 2 is a schematic diagram of another organic light-emitting apparatus that may include a compound and a compound formulation disclosed by the present disclosure.

DETAILED DESCRIPTION

OLEDs can be fabricated on various types of substrates such as glass, plastic, and metal foil. FIG. 1 schematically shows an organic light emitting device 100 without limitation. The figures are not necessarily drawn to scale. Some of the layers in the figures can also be omitted as needed. Device 100 may include a substrate 101, an anode 110, a hole injection layer 120, a hole transport layer 130, an electron blocking layer 140, an emissive layer 150, a hole blocking layer 160, an electron transport layer 170, an electron injection layer 180 and a cathode 190. Device 100 may be fabricated by depositing the layers described in order. The properties and functions of these various layers, as well as example materials, are described in more detail in U.S. Pat. No. 7,279,704 at cols. 6-10, the contents of which are incorporated by reference herein in its entirety.

More examples for each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference herein in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F₄-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference herein in its entirety. Examples of host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which is incorporated by reference herein in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference herein in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference herein in their entireties, disclose examples of cathodes including composite cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, electrically-conductive, sputter-deposited ITO layer. The theory and use of blocking layers are described in more detail in U.S. Pat. No. 6,097,147 and U.S. Patent Application Publication No. 2003/0230980, which are incorporated by reference herein in their entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference herein in its entirety. A description of protective layers may be found in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference herein in its entirety.

The layered structure described above is provided by way of non-limiting examples. Functional OLEDs may be achieved by combining the various layers described in different ways, or layers may be omitted entirely. It may also include other layers not specifically described. Within each layer, a single material or a mixture of multiple materials can be used to achieve optimum performance Any functional layer may include several sublayers. For example, the emissive layer may have two layers of different emitting materials to achieve desired emission spectrum.

In one embodiment, an OLED may be described as having an “organic layer” disposed between a cathode and an anode. This organic layer may comprise a single layer or multiple layers.

An OLED can be encapsulated by a barrier layer. FIG. 2 schematically shows an organic light emitting device 200 without limitation. FIG. 2 differs from FIG. 1 in that the organic light emitting device include a barrier layer 102, which is above the cathode 190, to protect it from harmful species from the environment such as moisture and oxygen. Any material that can provide the barrier function can be used as the barrier layer such as glass or organic-inorganic hybrid layers. The barrier layer should be placed directly or indirectly outside of the OLED device. Multilayer thin film encapsulation was described in U.S. Pat. No. 7,968,146, which is incorporated by reference herein in its entirety.

Devices fabricated in accordance with embodiments of the present disclosure can be incorporated into a wide variety of consumer products that have one or more of the electronic component modules (or units) incorporated therein. Some examples of such consumer products include flat panel displays, monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, smart phones, tablets, phablets, wearable devices, smart watches, laptop computers, digital cameras, camcorders, viewfinders, micro-displays, 3-D displays, vehicles displays, and vehicle tail lights.

The materials and structures described herein may be used in other organic electronic devices listed above.

As used herein, “top” means furthest away from the substrate, while “bottom” means closest to the substrate. Where a first layer is described as “disposed over” a second layer, the first layer is disposed further away from the substrate. There may be other layers between the first and second layers, unless it is specified that the first layer is “in contact with” the second layer. For example, a cathode may be described as “disposed over” an anode, even though there are various organic layers in between.

As used herein, “solution processible” means capable of being dissolved, dispersed, or transported in and/or deposited from a liquid medium, either in solution or suspension form.

A ligand may be referred to as “photoactive” when it is believed that the ligand directly contributes to the photoactive properties of an emissive material. A ligand may be referred to as “ancillary” when it is believed that the ligand does not contribute to the photoactive properties of an emissive material, although an ancillary ligand may alter the properties of a photoactive ligand.

It is believed that the internal quantum efficiency (IQE) of fluorescent OLEDs can exceed the 25% spin statistics limit through delayed fluorescence. As used herein, there are two types of delayed fluorescence, i.e. P-type delayed fluorescence and E-type delayed fluorescence. P-type delayed fluorescence is generated from triplet-triplet annihilation (TTA).

On the other hand, E-type delayed fluorescence does not rely on the collision of two triplets, but rather on the transition between the triplet states and the singlet excited states. Compounds that are capable of generating E-type delayed fluorescence are required to have very small singlet-triplet gaps to convert between energy states. Thermal energy can activate the transition from the triplet state back to the singlet state. This type of delayed fluorescence is also known as thermally activated delayed fluorescence (TADF). A distinctive feature of TADF is that the delayed component increases as temperature rises. If the reverse intersystem crossing rate is fast enough to minimize the non-radiative decay from the triplet state, the fraction of back populated singlet excited states can potentially reach 75%. The total singlet fraction can be 100%, far exceeding 25% of the spin statistics limit for electrically generated excitons.

E-type delayed fluorescence characteristics can be found in an exciplex system or in a single compound. Without being bound by theory, it is believed that E-type delayed fluorescence requires the luminescent material to have a small singlet-triplet energy gap (ΔE_(S-T)). Organic, non-metal containing, donor-acceptor luminescent materials may be able to achieve this. The emission in these materials is generally characterized as a donor-acceptor charge-transfer (CT) type emission. The spatial separation of the HOMO and LUMO in these donor-acceptor type compounds generally results in small ΔE_(S-T). These states may involve CT states. Generally, donor-acceptor luminescent materials are constructed by connecting an electron donor moiety such as amino- or carbazole-derivatives and an electron acceptor moiety such as N-containing six-membered aromatic rings.

Definition of Terms of Substituents

Halogen or halide—as used herein includes fluorine, chlorine, bromine, and iodine.

Alkyl—contemplates both straight and branched chain alkyl groups. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, neopentyl group, 1-methylpentyl group, 2-methylpentyl group, 1-pentylhexyl group, 1-butylpentyl group, 1-heptyloctyl group, and 3-methylpentyl group. Additionally, the alkyl group may be optionally substituted. The carbons in the alkyl chain can be replaced by other hetero atoms. Of the above, preferred are methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, and neopentyl group.

Cycloalkyl—as used herein contemplates cyclic alkyl groups. Preferred cycloalkyl groups are those containing 4 to 10 ring carbon atoms and include cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4,4-dimethylcylcohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl and the like. Additionally, the cycloalkyl group may be optionally substituted. The carbons in the ring can be replaced by other hetero atoms.

Alkenyl—as used herein contemplates both straight and branched chain alkene groups. Preferred alkenyl groups are those containing 2 to 15 carbon atoms. Examples of the alkenyl group include vinyl group, allyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1,3-butandienyl group, 1-methylvinyl group, styryl group, 2,2-diphenylvinyl group, 1,2-diphenylvinyl group, 1-methylallyl group, 1,1-dimethylallyl group, 2-methylallyl group, 1-phenylallyl group, 2-phenylallyl group, 3-phenylallyl group, 3,3-diphenylallyl group, 1,2-dimethylallyl group, 1-phenyll-butenyl group, and 3-phenyl-1-butenyl group. Additionally, the alkenyl group may be optionally substituted.

Alkynyl—as used herein contemplates both straight and branched chain alkyne groups. Preferred alkynyl groups are those containing 2 to 15 carbon atoms. Additionally, the alkynyl group may be optionally substituted.

Aryl or aromatic group—as used herein includes noncondensed and condensed systems. Preferred aryl groups are those containing six to sixty carbon atoms, preferably six to twenty carbon atoms, more preferably six to twelve carbon atoms. Examples of the aryl group include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene, and naphthalene. Additionally, the aryl group may be optionally substituted. Examples of the non-condensed aryl group include phenyl group, biphenyl-2-yl group, biphenyl-3-yl group, biphenyl-4-yl group, p-terphenyl-4-yl group, p-terphenyl-3-yl group, p-terphenyl-2-yl group, m-terphenyl-4-yl group, m-terphenyl-3-yl group, m-terphenyl-2-yl group, o-tolyl group, m-tolyl group, p-tolyl group, p-t-butylphenyl group, p-(2-phenylpropyl)phenyl group, 4′-methylbiphenylyl group, 4″-t-butyl p-terphenyl-4-yl group, o-cumenyl group, m-cumenyl group, p-cumenyl group, 2,3-xylyl group, 3,4-xylyl group, 2,5-xylyl group, mesityl group, and m-quarterphenyl group.

Heterocyclic group or heterocycle—as used herein includes aromatic and non-aromatic cyclic groups. Hetero-aromatic also means heteroaryl. Preferred non-aromatic heterocyclic groups are those containing 3 to 7 ring atoms which include at least one hetero atom such as nitrogen, oxygen, and sulfur. The heterocyclic group can also be an aromatic heterocyclic group having at least one heteroatom selected from nitrogen atom, oxygen atom, sulfur atom, and selenium atom.

Heteroaryl—as used herein includes noncondensed and condensed hetero-aromatic groups that may include from one to five heteroatoms. Preferred heteroaryl groups are those containing three to thirty carbon atoms, preferably three to twenty carbon atoms, more preferably three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine, and aza-analogs thereof. Additionally, the heteroaryl group may be optionally substituted.

Alkoxy—it is represented by —O-Alkyl. Examples and preferred examples thereof are the same as those described above. Examples of the alkoxy group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, and hexyloxy group. The alkoxy group having 3 or more carbon atoms may be linear, cyclic or branched.

Aryloxy—it is represented by —O-Aryl or —O-heteroaryl. Examples and preferred examples thereof are the same as those described above. Examples of the aryloxy group having 6 to 40 carbon atoms include phenoxy group and biphenyloxy group.

Arylalkyl—as used herein contemplates an alkyl group that has an aryl substituent. Additionally, the arylalkyl group may be optionally substituted. Examples of the arylalkyl group include benzyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylisopropyl group, 2-phenylisopropyl group, phenyl-t-butyl group, alpha.-naphthylmethyl group, 1-alpha.-naphthylethyl group, 2-alpha-naphthylethyl group, 1-alpha-naphthylisopropyl group, 2-alpha-naphthylisopropyl group, beta-naphthylmethyl group, 1-beta-naphthylethyl group, 2-beta-naphthylethyl group, 1-beta-naphthylisopropyl group, 2-beta-naphthylisopropyl group, p-methylbenzyl group, m-methylbenzyl group, o-methylbenzyl group, p-chlorobenzyl group, m-chlorobenzyl group, o-chlorobenzyl group, p-bromobenzyl group, m-bromobenzyl group, o-bromobenzyl group, p-iodobenzyl group, m-iodobenzyl group, o-iodobenzyl group, p-hydroxybenzyl group, m-hydroxybenzyl group, o-hydroxybenzyl group, p-aminobenzyl group, m-aminobenzyl group, o-aminobenzyl group, p-nitrobenzyl group, m-nitrobenzyl group, o-nitrobenzyl group, p-cyanobenzyl group, m-cyanobenzyl group, o-cyanobenzyl group, 1-hydroxy-2-phenylisopropyl group, and 1-chloro-2-phenylisopropyl group. Of the above, preferred are benzyl group, p-cyanobenzyl group, m-cyanobenzyl group, o-cyanobenzyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylisopropyl group, and 2-phenylisopropyl group.

The term “aza” in azafluorene, azaspirobifluorene, azadibenzofuran, aza-dibenzothiophene, etc. means that one or more of the C—H groups in the respective aromatic fragment are replaced by a nitrogen atom. For example, azatriphenylene encompasses dibenzo[f,h]quinoxaline, dibenzo[f,h]quinoline and other analogues with two or more nitrogens in the ring system. One of ordinary skill in the art can readily envision other nitrogen analogs of the aza-derivatives described above, and all such analogs are intended to be encompassed by the terms as set forth herein.

In the present disclosure, unless otherwise defined, when any term of the group consisting of substituted alkyl, substituted cycloalkyl, substituted heteroalkyl, substituted arylalkyl, substituted alkoxy, substituted aryloxy, substituted alkenyl, substituted aryl, substituted heteroaryl, substituted alkylsilyl, substituted arylsilyl, substituted amino, substituted acyl, substituted carbonyl, substituted carboxylic acid group, substituted ester group, substituted sulfinyl, substituted sulfonyl and substituted phosphino is used, it means that any group of alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, alkenyl, aryl, heteroaryl, alkylsilyl, arylsilyl, amino, acyl, carbonyl, carboxylic acid group, ester group, sulfinyl, sulfonyl and phosphino may be substituted with one or more groups selected from the group consisting of deuterium, an unsubstituted alkyl having 1 to 20 carbon atoms, an unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, an unsubstituted heteroalkyl having 1 to 20 carbon atoms, an unsubstituted arylalkyl having 7 to 30 carbon atoms, an unsubstituted alkoxy having 1 to 20 carbon atoms, an unsubstituted aryloxy having 6 to 30 carbon atoms, an unsubstituted alkenyl having 2 to 20 carbon atoms, an unsubstituted aryl having 6 to 30 carbon atoms or preferably, an unsubstituted aryl having 6 to 12 carbon atoms, an unsubstituted heteroaryl having 3 to 30 carbon atoms or preferably, an unsubstituted heteroaryl having 3 to 12 carbon atoms, an unsubstituted alkylsilyl having 3 to 20 carbon atoms, an unsubstituted arylsilyl group having 6 to 20 carbon atoms, an unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a thiol group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof.

It is to be understood that when a molecular fragment is described as being a substituent or otherwise attached to another moiety, its name may be written as if it were a fragment (e.g. phenyl, phenylene, naphthyl, dibenzofuryl) or as if it were the whole molecule (e.g. benzene, naphthalene, dibenzofuran). As used herein, these different ways of designating a substituent or an attached fragment are considered to be equivalent.

In the compounds mentioned in the present disclosure, hydrogen atoms can be partially or fully replaced by deuterium. Other atoms such as carbon and nitrogen can also be replaced by their other stable isotopes. The replacement by other stable isotopes in the compounds may be preferred due to its enhancements of device efficiency and stability. In the compounds mentioned in the present disclosure, a deuterated substituent, such as deuterated methyl, refers to that at least one hydrogen atom in the substituent (methyl) is replaced by deuterium.

In the compounds mentioned in the present disclosure, multi-substitution refers to a range that includes a di-substitution, up to the maximum available substitution. When a substitution in the compounds mentioned in the present disclosure represents multi-substitution (including di-, tri-, and tetra-substitution etc.), that means the substituent may exist at a plurality of available substitution positions on its linking structure, the substituents present at a plurality of available substitution positions may have the same structure or different structures.

In the compounds mentioned in the present disclosure, adjacent substituents in the compounds cannot be joined to form a ring unless otherwise explicitly defined, for example, adjacent substituents can be optionally joined to form a ring. In the compounds mentioned in the present disclosure, that adjacent substituents can be optionally joined to form a ring includes a case where adjacent substituents may be joined to form a ring and a case where adjacent substituents are not joined to form a ring. When adjacent substituents can be optionally joined to form a ring, the ring formed may be monocyclic or polycyclic, as well as alicyclic, heteroalicyclic, aromatic or heteroaromatic. In such expression, adjacent substituents may refer to substituents bonded to the same atom, substituents bonded to carbon atoms which are directly bonded to each other, or substituents bonded to carbon atoms which are more distant from each other. Preferably, adjacent substituents refer to substituents bonded to the same carbon atom and substituents bonded to carbon atoms which are directly bonded to each other.

The expression that two adjacent substituents can be optionally joined to form a ring is also intended to mean that two substituents bonded to the same carbon atom are joined to each other via a chemical bond to form a ring, which can be exemplified by the following formula:

The expression that two adjacent substituents can be optionally joined to form a ring is also intended to mean that two substituents bonded to carbon atoms which are directly bonded to each other are joined to each other via a chemical bond to form a ring, which can be exemplified by the following formula:

Furthermore, the expression that two adjacent substituents can be optionally joined to form a ring is also intended to mean that, in the case where one of the two substituents bonded to carbon atoms which are directly bonded to each other represents hydrogen, the second substituent is bonded at a position at which the hydrogen atom is bonded, thereby forming a ring. This is exemplified by the following formula:

According to an embodiment of the present disclosure, disclosed is a compound having Formula 1:

-   -   in Formula 1,     -   A is substituted or unsubstituted aryl having 10 to 60 ring         carbon atoms or substituted or unsubstituted heteroaryl having         10 to 60 ring atoms;     -   n is an integer greater than or equal to 1, m is an integer         greater than or equal to 0, and n+m is greater than or equal to         2; when n is greater than or equal to 2, B may be the same or         different structures; when m is greater than or equal to 2, E         may be the same or different structures;     -   E has a structure represented by Formula 2:

-   -   in Formula 2, * represents a position where E is joined to A;     -   Ar and Ar₁ are each independently selected from the group         consisting of: substituted or unsubstituted aryl having 6 to 30         ring carbon atoms and substituted or unsubstituted heteroaryl         having 3 to 30 ring atoms;     -   B has a structure represented by Formula 3:

-   -   in Formula 3, * represents a position where B is joined to A;     -   wherein R is selected from the group consisting of: substituted         or unsubstituted aryl having 6 to 30 ring carbon atoms and         substituted or unsubstituted heteroaryl having 3 to 30 ring         atoms; and when R is selected from aryl, R is not substituted or         unsubstituted naphthyl;     -   wherein Ar₂ has a structure represented by Formula 4:

-   -   and Ar₂ includes only one fluorene ring structure, azafluorene         ring structure, spirobifluorene ring structure, or         azaspirobifluorene ring structure;     -   in Formula 4, * represents a position where Ar₂ is joined to N         shown in Formula 3; X is C or Si;     -   L is selected from a single bond, substituted or unsubstituted         arylene having 6 to 60 carbon atoms, or substituted or         unsubstituted heteroarylene having 3 to 60 carbon atoms;     -   X₁ to X₈ are each independently selected from C, CR′ or N, and         two adjacent C (referring to two C directly bonded to each         other) are present in X₁ to X₄ (such as X₁ and X₂, X₂ and X₃, or         X₃ and X₄), wherein one of the two adjacent C is joined to L,         and the other one of the two adjacent C is joined to R″;     -   wherein R_(a), R_(b), and R′ are each independently selected         from the group consisting of: hydrogen, deuterium, halogen,         substituted or unsubstituted alkyl having 1 to 20 carbon atoms,         substituted or unsubstituted cycloalkyl having 3 to 20 ring         carbon atoms, substituted or unsubstituted heteroalkyl having 1         to 20 carbon atoms, substituted or unsubstituted arylalkyl         having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy         having 1 to 20 carbon atoms, substituted or unsubstituted         aryloxy having 6 to 30 carbon atoms, substituted or         unsubstituted alkenyl having 2 to 20 carbon atoms, substituted         or unsubstituted aryl having 6 to 30 carbon atoms, substituted         or unsubstituted heteroaryl having 3 to 30 carbon atoms,         substituted or unsubstituted alkylsilyl having 3 to 20 carbon         atoms, substituted or unsubstituted arylsilyl having 6 to 20         carbon atoms, substituted or unsubstituted amino having 0 to 20         carbon atoms, an acyl group, a carbonyl group, a carboxylic acid         group, an ester group, a nitrile group, an isonitrile group, a         thiol group, a sulfinyl group, a sulfonyl group, a phosphino         group, and combinations thereof;     -   wherein R″ is each independently selected from the group         consisting of: deuterium, halogen, substituted or unsubstituted         alkyl having 1 to 20 carbon atoms, substituted or unsubstituted         cycloalkyl having 3 to 20 ring carbon atoms, substituted or         unsubstituted heteroalkyl having 1 to 20 carbon atoms,         substituted or unsubstituted arylalkyl having 7 to 30 carbon         atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon         atoms, substituted or unsubstituted aryloxy having 6 to 30         carbon atoms, substituted or unsubstituted alkenyl having 2 to         20 carbon atoms, substituted or unsubstituted aryl having 6 to         30 carbon atoms, substituted or unsubstituted heteroaryl having         3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl         having 3 to 20 carbon atoms, substituted or unsubstituted         arylsilyl having 6 to 20 carbon atoms, substituted or         unsubstituted amino having 0 to 20 carbon atoms, an acyl group,         a carbonyl group, a carboxylic acid group, an ester group, a         nitrile group, an isonitrile group, a thiol group, a sulfinyl         group, a sulfonyl group, a phosphino group, and combinations         thereof; and     -   wherein in Formula 4, substituents R_(a) and R_(b) can be         optionally joined to form a ring, and two adjacent substituents         R′ can be optionally joined to form a ring.

In this embodiment, in Formula 4, only substituents R_(a) and R_(b), and two adjacent substituents R′ can be optionally joined to form a ring. Other substituents are not joined to form a ring, for example, adjacent substituents R′ and R″ are not joined to form a ring. In some cases, only part of two adjacent substituents R may be optionally joined to form a ring. For example, two adjacent R′ in only X₅ to X₈ are optionally joined to form a ring. In another example, two adjacent R′ in X₅ to X₄ are not joined to form a ring. In some cases, none of substituents in Formula 4 may be joined to form a ring.

In this embodiment, when R is selected from the aryl, R is not substituted or unsubstituted naphthyl, which means that the above Formula 3 does not include the following structure:

In the structure of a or b, R_(N) may represent mono-substitution, multi-substitution, or non-substitution. The range of a substituent R_(N) is not particularly limited. In some cases, the range of R_(N) may be the same as the range of R defined in this embodiment.

In this embodiment, the expression that Ar₂ includes only one fluorene ring structure, azafluorene ring structure, spirobifluorene ring structure, or azaspirobifluorene ring structure refers to that Formula 4 includes only one in terms of the sum of numbers of the four ring structures, i.e., the fluorene ring structure, the azafluorene ring structure, the spirobifluorene ring structure, and the azaspirobifluorene ring structure. The only one structure included is a ring structure containing atoms or groups comprising X₁ to X₈ and X (X is C). Therefore, it is to be understood that in the above Formula 4, none of L, R′ and R″ includes a fluorene ring structure, an azafluorene ring structure, a spirobifluorene ring structure, or an azaspirobifluorene ring structure. It is to be noted that even if one or more arbitrary substituents are present in the fluorene ring structure, the azafluorene ring structure, the spirobifluorene ring structure, or the azaspirobifluorene ring structure, such structures will still be counted into the number of the ring structures included in Ar₂.

In some embodiments, R in Formula 3 only includes at most one fluorene ring structure, azafluorene ring structure, spirobifluorene ring structure, or azaspirobifluorene ring structure. Even if one or more arbitrary substituents are present in the fluorene ring structure, the azafluorene ring structure, the spirobifluorene ring structure, or the azaspirobifluorene ring structure, such structures will still be counted into the number of the ring structures included in R. In this case, R includes one or less the above ring structure in total.

According to an embodiment of the present disclosure, A in Formula 1 is substituted or unsubstituted aryl having 10 to 40 ring atoms or substituted or unsubstituted heteroaryl having 10 to 40 ring atoms. Further, A in Formula 1 is substituted or unsubstituted aryl having 10 to 30 ring atoms or substituted or unsubstituted heteroaryl having 10 to 30 ring atoms. Further, A in Formula 1 is substituted or unsubstituted aryl having 10 to 20 ring atoms or substituted or unsubstituted heteroaryl having 10 to 20 ring atoms.

According to an embodiment of the present disclosure, in Formula 1, n is 1, and m is 1; or n is greater than or equal to 2, and m is 0.

According to an embodiment of the present disclosure, A in Formula 1 is selected from a structure represented by any one of Formula Ito Formula IX:

-   -   in Formula Ito Formula IX, n of R₁ to R, have the structure of B         represented by Formula 3, and m of R₁ to R_(i) have the         structure of E represented by Formula 2;     -   n is 1, 2, 3, or 4, m is 0, 1, 2, 3, or 4, and n+m is greater         than or equal to 2;     -   R_(i) represents the R with the largest number in any one of         Formula Ito Formula IX;     -   the rest of R₁ to R_(i) are each independently selected from the         group consisting of: hydrogen, deuterium, halogen, substituted         or unsubstituted alkyl having 1 to 20 carbon atoms, substituted         or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms,         substituted or unsubstituted heteroalkyl having 1 to 20 carbon         atoms, substituted or unsubstituted arylalkyl having 7 to 30         carbon atoms, substituted or unsubstituted alkoxy having 1 to 20         carbon atoms, substituted or unsubstituted aryloxy having 6 to         30 carbon atoms, substituted or unsubstituted aryl having 6 to         30 carbon atoms, substituted or unsubstituted heteroaryl having         3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl         having 3 to 20 carbon atoms, substituted or unsubstituted         arylsilyl having 6 to 20 carbon atoms, and combinations thereof;     -   X_(a) and X_(b) are each independently selected from the group         consisting of: CR_(x)R_(y), SiR_(x)R_(y), NR_(x), O, S, and Se;     -   R_(x) and R_(y) are each independently selected from the group         consisting of: hydrogen, deuterium, halogen, substituted or         unsubstituted alkyl having 1 to 20 carbon atoms, substituted or         unsubstituted cycloalkyl having 3 to 20 ring carbon atoms,         substituted or unsubstituted heteroalkyl having 1 to 20 carbon         atoms, substituted or unsubstituted arylalkyl having 7 to 30         carbon atoms, substituted or unsubstituted alkoxy having 1 to 20         carbon atoms, substituted or unsubstituted aryloxy having 6 to         30 carbon atoms, substituted or unsubstituted alkenyl having 2         to 20 carbon atoms, substituted or unsubstituted aryl having 6         to 30 carbon atoms, substituted or unsubstituted heteroaryl         having 3 to 30 carbon atoms, substituted or unsubstituted         alkylsilyl having 3 to 20 carbon atoms, substituted or         unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted         or unsubstituted amino having 0 to 20 carbon atoms, an acyl         group, a carbonyl group, a carboxylic acid group, an ester         group, a nitrile group, an isonitrile group, a thiol group, a         sulfinyl group, a sulfonyl group, a phosphino group, and         combinations thereof; and     -   substituents R_(x) and R_(y) can be optionally joined to form a         ring.

In this embodiment, taking Formula I as an example, R_(i) represents the R with the largest number in Formula I (i.e., R₁₀), n of R₁ to R₁₀ have the structure of B represented by Formula 3, and m of R₁ to R₁₀ have the structure of E represented by Formula 2. In another example, in Formula I, R₁ has the structure of B represented by Formula 3, R₆ has the structure of E represented by Formula 2, the rest of R₁ to R₁₀ are each independently selected from the group defined above, which means that R₂ to R₅ and R₇ to R₁₀ are each independently selected from the group defined above. This is also suitable for Formula II to Formula IX.

According to an embodiment of the present disclosure, for Formula I, R₂, R₄-R₅, R₇, and R₉-R₁₀ are each a hydrogen atom, and substituent R₃ and R₈ are each independently selected from hydrogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, or substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms.

According to an embodiment of the present disclosure, for Formula II, R₁-R₂, R₄-R₅, R₇-R₈, and R₁₀-R₁₁ are each a hydrogen atom, and substituent R₃ and R₉ are each independently selected from hydrogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, or substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms.

According to an embodiment of the present disclosure, in Formula I to Formula IX, two of R₁ to R_(i) have the structure of B represented by Formula 3, and none of R₁ to R_(i) has the structure of E represented by Formula 2, wherein R_(i) represents the R with the largest number in any one of Formula Ito Formula IX.

According to an embodiment of the present disclosure, the compound has a structure represented by one of Formula 5 to Formula 13:

-   -   in Formula 5 to Formula 13,     -   R₁ to R₁₂ are each independently selected from the group         consisting of: hydrogen, deuterium, halogen, substituted or         unsubstituted alkyl having 1 to 20 carbon atoms, substituted or         unsubstituted cycloalkyl having 3 to 20 ring carbon atoms,         substituted or unsubstituted heteroalkyl having 1 to 20 carbon         atoms, substituted or unsubstituted arylalkyl having 7 to 30         carbon atoms, substituted or unsubstituted alkoxy having 1 to 20         carbon atoms, substituted or unsubstituted aryloxy having 6 to         30 carbon atoms, substituted or unsubstituted aryl having 6 to         30 carbon atoms, substituted or unsubstituted heteroaryl having         3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl         having 3 to 20 carbon atoms, substituted or unsubstituted         arylsilyl having 6 to 20 carbon atoms, and combinations thereof;     -   X_(a)and X_(b) are each independently selected from the group         consisting of: CR_(x)R_(y), SiR_(x)R_(y), NR_(x), O, S, and Se;

R_(x) and R_(y) are each independently selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a thiol group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;

-   -   substituents R_(x) and R_(y) can be optionally joined to form a         ring; and     -   R, R_(a), R_(b), R″, L, X, and X₁ to X₈ have same ranges as         defined in Formula 3 and Formula 4 in the embodiments described         above.

According to an embodiment of the present disclosure, for Formula 5, R₂, R₄-R₅, R₇, and R₉-R₁₀ are each a hydrogen atom, and substituent R₃ and R₈ are each independently selected from hydrogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, or substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms.

According to an embodiment of the present disclosure, in Formula 5 to Formula 13, each L is joined to X₂.

According to an embodiment of the present disclosure, in Formula 5 to Formula 13, each L is joined to X₃.

According to an embodiment of the present disclosure, L in Formula 4 is selected from a single bond, substituted or unsubstituted arylene having 6 to 30 carbon atoms, or substituted or unsubstituted heteroarylene having 3 to 30 carbon atoms; further, L in Formula 4 is selected from a single bond, substituted or unsubstituted arylene having 6 to 20 carbon atoms, or substituted or unsubstituted heteroarylene having 3 to 20 carbon atoms; further, L in Formula 4 is selected from a single bond, substituted or unsubstituted arylene having 6 to 12 carbon atoms, or substituted or unsubstituted heteroarylene having 3 to 12 carbon atoms; further, L is selected from a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, or substituted or unsubstituted naphthylene.

According to an embodiment of the present disclosure, X₁ to X₈ are each independently selected from C or CR, wherein R is each independently selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 10 ring carbon atoms, substituted or unsubstituted aryl having 6 to 12 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 12 carbon atoms, a nitrile group, and combinations thereof.

According to an embodiment of the present disclosure, X₁ to X₈ are each independently selected from C or CR, wherein R is each independently selected from hydrogen, deuterium, fluorine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, cyclohexyl, phenyl, or cyano.

According to an embodiment of the present disclosure, R″ is selected from halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, or substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms.

According to an embodiment of the present disclosure, R″ is selected from fluorine, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, t-butyl, cyclopentyl, neopentyl, cyclohexyl, 4,4-dimethylcyclohexyl, deuterated methyl, deuterated ethyl, deuterated n-propyl, deuterated isopropyl, deuterated cyclopropyl, deuterated n-butyl, deuterated isobutyl, deuterated t-butyl, deuterated cyclopentyl, deuterated neopentyl, deuterated cyclohexyl, or deuterated 4,4-dimethylcyclohexyl.

According to an embodiment of the present disclosure, R_(a) and R_(b) are each independently selected from substituted or unsubstituted alkyl having 1 to 6 carbon atoms or substituted or unsubstituted cycloalkyl having 3 to 10 ring carbon atoms, and R_(a) and R_(b) are not joined to form a ring.

According to an embodiment of the present disclosure, R_(a) and R_(b) are each methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or t-butyl, and R_(a) and R_(b) are not joined to form a ring.

According to an embodiment of the present disclosure, R in Formula 3 has a structure represented by Formula 17:

-   -   in Formula 17, * represents a position wherein R is joined to N         shown in Formula 3;     -   wherein the ring Ar₃ is aryl having 6 to 30 ring carbon atoms or         heteroaryl having 3 to 30 ring atoms; and when the ring Ar₃ is         aryl, the ring Ar₃ is not a naphthalene ring;     -   wherein R_(e) represents mono-substitution, multi-substitution,         or non-substitution; and R_(e) is selected from the group         consisting of: hydrogen, deuterium, halogen, substituted or         unsubstituted alkyl having 1 to 20 carbon atoms, substituted or         unsubstituted cycloalkyl having 3 to 20 ring carbon atoms,         substituted or unsubstituted heteroalkyl having 1 to 20 carbon         atoms, substituted or unsubstituted arylalkyl having 7 to 30         carbon atoms, substituted or unsubstituted alkoxy having 1 to 20         carbon atoms, substituted or unsubstituted aryloxy having 6 to         30 carbon atoms, substituted or unsubstituted alkenyl having 2         to 20 carbon atoms, substituted or unsubstituted aryl having 6         to 30 carbon atoms, substituted or unsubstituted heteroaryl         having 3 to 30 carbon atoms, substituted or unsubstituted         alkylsilyl having 3 to 20 carbon atoms, substituted or         unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted         or unsubstituted amino having 0 to 20 carbon atoms, an acyl         group, a carbonyl group, a carboxylic acid group, an ester         group, a nitrile group, an isonitrile group, a thiol group, a         sulfinyl group, a sulfonyl group, a phosphino group, and         combinations thereof.

According to an embodiment of the present disclosure, the substituent R_(e) in Formula 17 is selected from the group consisting of: halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a thiol group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof.

According to an embodiment of the present disclosure, the substituent R_(e) in Formula 17 is selected from the group consisting of: fluorine, nitrile, isonitrile, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, and substituted or unsubstituted aryl having 6 to 12 carbon atoms.

According to an embodiment of the present disclosure, R in Formula 3 has a structure represented by Formula 14:

-   -   wherein * represents a position wherein R is joined to N in         Formula 3;     -   wherein the ring Ar₃ is aryl having 6 to 30 ring carbon atoms or         heteroaryl having 3 to 30 ring atoms; and when the ring Ar₃ is         aryl, the ring Ar₃ is not a naphthalene ring structure;     -   R_(c) represents ortho-substitution of the position wherein R is         joined to N in Formula 3, and R_(d) represents         mono-substitution, multi-substitution, or non-substitution;     -   wherein R_(c) is selected from the group consisting of:         deuterium, halogen, substituted or unsubstituted alkyl having 1         to 20 carbon atoms, substituted or unsubstituted cycloalkyl         having 3 to 20 ring carbon atoms, substituted or unsubstituted         heteroalkyl having 1 to 20 carbon atoms, substituted or         unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted         or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted         or unsubstituted aryloxy having 6 to 30 carbon atoms,         substituted or unsubstituted alkenyl having 2 to 20 carbon         atoms, substituted or unsubstituted aryl having 6 to 30 carbon         atoms, substituted or unsubstituted heteroaryl having 3 to 30         carbon atoms, substituted or unsubstituted alkylsilyl having 3         to 20 carbon atoms, substituted or unsubstituted arylsilyl         having 6 to 20 carbon atoms, substituted or unsubstituted amino         having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a         carboxylic acid group, an ester group, a nitrile group, an         isonitrile group, a thiol group, a sulfinyl group, a sulfonyl         group, a phosphino group, and combinations thereof;     -   wherein R_(d) is each independently selected from the group         consisting of: hydrogen, deuterium, halogen, substituted or         unsubstituted alkyl having 1 to 20 carbon atoms, substituted or         unsubstituted cycloalkyl having 3 to 20 ring carbon atoms,         substituted or unsubstituted heteroalkyl having 1 to 20 carbon         atoms, substituted or unsubstituted arylalkyl having 7 to 30         carbon atoms, substituted or unsubstituted alkoxy having 1 to 20         carbon atoms, substituted or unsubstituted aryloxy having 6 to         30 carbon atoms, substituted or unsubstituted alkenyl having 2         to 20 carbon atoms, substituted or unsubstituted aryl having 6         to 30 carbon atoms, substituted or unsubstituted heteroaryl         having 3 to 30 carbon atoms, substituted or unsubstituted         alkylsilyl having 3 to 20 carbon atoms, substituted or         unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted         or unsubstituted amino having 0 to 20 carbon atoms, an acyl         group, a carbonyl group, a carboxylic acid group, an ester         group, a nitrile group, an isonitrile group, a thiol group, a         sulfinyl group, a sulfonyl group, a phosphino group, and         combinations thereof.

In this embodiment, the ring Ar₃ in Formula 14 refers to a ring structure composed of only ring atoms (which may be all ring carbon atoms or may also include ring heteroatoms). All substituents that have to be present and might be present on the ring Ar₃ are particularly represented by R_(c) and R_(d) in Formula 14. When the ring Ar₃ is aryl having 6 to 30 ring carbon atoms or heteroaryl having 3 to 30 ring atoms, it means that the ring Ar₃ is an aryl ring structure comprising 6 to 30 ring carbon atoms or a heteroaryl ring structure comprising 3 to 30 ring atoms. Therefore, that the ring Ar₃ is not a naphthalene ring includes that the ring Ar₃ is not an unsubstituted or optionally substituted naphthalene ring structure. Formula 14 does not include the following structures:

In the three structures, R_(n2) may represent mono-substitution, multi-substitution, or non-substitution. Ranges of substituents R_(n1) and R_(n2) are not particularly limited. For example, a range of R_(n1) may be the same as a range of R_(c) defined in this embodiment, and a range of R_(n2) may be the same as a range of R_(d) defined in this embodiment.

According to an embodiment of the present disclosure, the ring Ar₃ is selected from any one of the following ring structures: a benzene ring, a triphenylene ring, a tetraphenylene ring, a phenanthrene ring, an anthracene ring, an indene ring, a fluorene ring, a chrysene ring, an indole ring, a carbazole ring, a benzofuran ring, a dibenzofuran ring, a benzosilole ring, a dibenzosilole ring, a benzothiophene ring, a dibenzothiophene ring, a dibenzoselenophene ring, or aza-structures of any one of the above ring structures. In this embodiment, for example, when the ring Ar₃ is selected from a benzene ring, the structure of Formula 14 is accordingly

wherein R_(c) and R_(d) are defined as in Formula 14. When the ring Ar₃ is selected from other ring structures, the cases are similar to the example of the benzene ring. When the ring Ar₃ is selected from an azabenzene ring, it refers to that one or more C—H groups in the benzene ring are replaced by a nitrogen atom. Accordingly, the structure of Formula 14 is

or other structures. When the ring Ar₃ is selected from other aza-ring structures, the cases are similar to the example of the benzene ring.

According to an embodiment of the present disclosure, R_(d) represents non-substitution, or R_(d) represents mono-substitution and R_(d) is selected from the group consisting of: substituted or unsubstituted aryl having 6 to 12 carbon atoms and substituted or unsubstituted heteroaryl having 3 to 12 carbon atoms; preferably, R_(d) is selected from phenyl, biphenyl, or terphenyl.

According to an embodiment of the present disclosure, R_(c) is selected from methyl, deuterated methyl, ethyl, deuterated ethyl, n-propyl, deuterated n-propyl, isopropyl, deuterated isopropyl, cyclopropyl, deuterated cyclopropyl, n-butyl, deuterated n-butyl, isobutyl, deuterated isobutyl, t-butyl, deuterated t-butyl, cyclopentyl, deuterated cyclopentyl, neopentyl, deuterated neopentyl, cyclohexyl, deuterated cyclohexyl, 4,4-dimethylcyclohexyl, or deuterated 4,4-dimethylcyclohexyl.

According to an embodiment of the present disclosure, B is selected from B-1-1 to B-1-72, B-2-1 to B-2-218, B-3-1 to B-3-235, B-4-1 to B-4-72, B-5-1 to B-5-72, or B-6-1 to B-6-18 whose specific structures are as shown in claim 15.

According to an embodiment of the present disclosure, the compound is selected from

A-(—B)_(n)

compounds 1 to 2398 which have a structure represented by Formula 15: Formula 15, wherein n in the structure represented by Formula 15 equals 2, two B are the same, and A has a structure selected from A₁ to A₁₀:

-   -   wherein in the structures of A₁ to A₁₀, * represents a position         wherein the group B is joined;     -   the structure of B is selected from B-1-1 to B-1-72, B-2-1 to         B-2-218, B-3-1 to B-3-235, B-4-1 to B-4-72, B-5-1 to B-5-72, or         B-6-1 to B-6-18 whose specific structures are as shown in claim         15. The compound is selected from the compounds 1 to 2398 whose         specific structures are as shown in claim 16.

According to an embodiment of the present disclosure, hydrogen in the compounds 1 to 2398 may be partially or fully deuterated.

According to an embodiment of the present disclosure, the compound has a molecular weight which is less than 2500, further has a molecular weight which is less than 2000, and more further has a molecular weight which is less than 1500. Such small molecular compounds are more applicable to vacuum evaporation.

According to an embodiment of the present disclosure, further disclosed is an electroluminescent device, including:

-   -   an anode,     -   a cathode, and     -   an organic layer disposed between the anode and the cathode,         wherein the organic layer includes the compound represented by         Formula 1;     -   wherein the compound represented by Formula 1 has specific         structures as shown in any one of the embodiments described         above.

According to an embodiment of the present disclosure, the organic layer is a light-emitting layer, and the compound is a light-emitting material.

According to an embodiment of the present disclosure, the light-emitting layer further includes a compound represented by Formula 16:

-   -   wherein R_(g1) to R_(g8) are each independently selected from         the group consisting of: hydrogen, deuterium, halogen,         substituted or unsubstituted alkyl having 1 to 20 carbon atoms,         substituted or unsubstituted cycloalkyl having 3 to 20 ring         carbon atoms, substituted or unsubstituted heteroalkyl having 1         to 20 carbon atoms, substituted or unsubstituted arylalkyl         having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy         having 1 to 20 carbon atoms, substituted or unsubstituted         aryloxy having 6 to 30 carbon atoms, substituted or         unsubstituted alkenyl having 2 to 20 carbon atoms, substituted         or unsubstituted aryl having 6 to 30 carbon atoms, substituted         or unsubstituted heteroaryl having 3 to 30 carbon atoms,         substituted or unsubstituted alkylsilyl having 3 to 20 carbon         atoms, substituted or unsubstituted arylsilyl having 6 to 20         carbon atoms, substituted or unsubstituted amino having 0 to 20         carbon atoms, an acyl group, a carbonyl group, a carboxylic acid         group, an ester group, a nitrile group, an isonitrile group, a         thiol group, a sulfinyl group, a sulfonyl group, a phosphino         group, and combinations thereof; and     -   wherein R_(g9) to R_(g10) are each independently selected from         substituted or unsubstituted aryl having 6 to 30 carbon atoms or         substituted or unsubstituted heteroaryl having 3 to 30 carbon         atoms.

According to another embodiment of the present disclosure, further disclosed is a compound formulation which includes the compound represented by Formula 1. The compound has specific structures as shown in any one of the embodiments described above.

Combination with Other Materials

The materials described in the present disclosure for a particular layer in an organic light emitting device can be used in combination with various other materials present in the device. The combinations of these materials are described in more detail in U.S. Pat. App. No. 20160359122 at paragraphs 0132-0161, which is incorporated by reference herein in its entirety. The materials described or referred to the disclosure are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination.

The materials described herein as useful for a particular layer in an organic light emitting device may be used in combination with a variety of other materials present in the device. For example, dopants disclosed herein may be used in combination with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes and other layers that may be present. The combination of these materials is described in detail in paragraphs 0080-0101 of U.S. Pat. App. No. 20150349273, which is incorporated by reference herein in its entirety. The materials described or referred to the disclosure are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination.

In the embodiments of material synthesis, all reactions were performed under nitrogen protection unless otherwise stated. All reaction solvents were anhydrous and used as received from commercial sources. Synthetic products were structurally confirmed and tested for properties using one or more conventional equipment in the art (including, but not limited to, nuclear magnetic resonance instrument produced by BRUKER, liquid chromatograph produced by SHIMADZU, liquid chromatograph-mass spectrometry produced by SHIMADZU, gas chromatograph-mass spectrometry produced by SHIMADZU, differential Scanning calorimeters produced by SHIMADZU, fluorescence spectrophotometer produced by SHANGHAI LENGGUANG TECH., electrochemical workstation produced by WUHAN CORRTEST, and sublimation apparatus produced by ANHUI BEQ, etc.) by methods well known to the persons skilled in the art. In the embodiments of the device, the characteristics of the device were also tested using conventional equipment in the art (including, but not limited to, evaporator produced by ANGSTROM ENGINEERING, optical testing system produced by SUZHOU FATAR, life testing system produced by SUZHOU FATAR, and ellipsometer produced by BEIJING ELLITOP, etc.) by methods well known to the persons skilled in the art. As the persons skilled in the art are aware of the above-mentioned equipment use, test methods and other related contents, the inherent data of the sample can be obtained with certainty and without influence, so the above related contents are not further described in this patent.

MATERIAL SYNTHESIS EXAMPLE

A method for preparing a compound in the present disclosure is not limited herein. Typically, the following compounds are taken as examples without limitations, and synthesis routes and preparation methods thereof are described below.

Synthesis Example 1: Synthesis of Compound 339

Step 1:

9,9-Dimethyl-9H-fluoren-2-amine (200 g, 0.96 mol) was dissolved in 2 L of dimethyl formamide (DMF) and cooled to 0° C., and then N-bromosuccinimide (190 g, 1.06 mol) was added portion-wise into the reaction solution, slowly warmed to room temperature, and stirred overnight. After the reaction was finished, most of dimethyl formamide was removed through rotary evaporation, and a large amount of water was added. The solution was extracted with dichloromethane (DCM), and then the organic phases were concentrated through rotary evaporation to be nearly saturated. The solution was filtered with silica gel powder and washed with PE, and the filtrate was concentrated through rotary evaporation and crystallized from PE to obtain the product, 3-bromo-9,9-dimethyl-9H-fluoren-2-amine (259 g with a yield of 94%).

Step 2:

3-Bromo-9,9-dimethyl-9H-fluoren-2-amine (259 g) was dissolved in 1.5 L of 10% concentrated sulfuric acid solution, stirred at room temperature for 1 h, and then cooled to 0° C. NaNO₂ (73 g, 1.06 mol) solids were added portion-wise. After the reaction mixture was stirred at low temperature for 1 h, KI (634 g, 3.82 mol) was slowly added portion-wise. After the reaction mixture was stirred overnight at room temperature, a saturated solution of sodium thiosulfate was added and stirred for 10 min. The solution was extracted three times with DCM. Then the organic phases were subjected to rotary evaporation to dryness, and purified through column chromatography (with PE as an eluent) to obtain the product, 3-bromo-2-iodo-9,9-dimethyl-9H-fluorene (240 g with a yield of 67%).

Step 3:

Under nitrogen protection, 3-bromo-2-iodo-9,9-dimethyl-9H-fluorene (240 g, 0.6 mol) was dissolved in 1 L of anhydrous tetrahydrofuran and cooled to −78° C. Isopropylmagnesium chloride (1.3M, 0.66 mol) was slowly added and reacted at low temperature for 1 h. iPrOBpin (148.8 g, 0.8 mol) was added, slowly warmed to room temperature, and reacted overnight. After the reaction was finished, water was added to quench the reaction. The aqueous phase was extracted three times with DCM. The organic phases were combined and filtered through Celite. After silica gel powder was added, samples were dry-mixed and subjected to column chromatography to obtain the product, (3-bromo-9,9-dimethyl-9H-fluoren-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (100 g with a yield of 42%).

Step 4:

Under nitrogen protection, (3-bromo-9,9-dimethyl-9H-fluoren-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (100 g, 250 mmol) was dissolved in 1 L of toluene/ethanol/water (at a volume ratio of 5:2:2), tetra(triphenylphosphine)palladium (5.5 g, 5 mmol), iodomethane (1.6 g, 750 mmol), and potassium carbonate (69 g, 500 mmol) were added, and the reaction was heated to 100° C. and stirred for 4 h. After the reaction was cooled to room temperature, layers were separated, the aqueous phase was extracted three times with DCM, and the organic phases were combined. After silica gel powder was added, samples were dry-loaded and separated through column chromatography using PE. The obtained crude product was crystallized from PE to finally obtain 3-bromo-2,9,9-trimethyl-9H-fluorene (66.87 g with a yield of 93.2%).

Step 5:

Pd₂(dba)₃ (2.05 g, 2.24 mmol) and BINAP (2.98 g, 4.48 mmol) were put into a 500 mL three-neck flask, and toluene (200 mL) was added. The solution was purged with N₂ for 20 min until the color no longer changed, and 3-bromo-2,9,9-trimethyl-9H-fluorene (12.6 g, 44 mmol), [1,1′-biphenyl]-3-amine (11.1 g, 66 mmol), and sodium tert-butoxide (12.86 g, 134 mmol) were sequentially added. N₂ was continued to be introduced for 10 min and the system was heated to 110° C. until 3-bromo-2,9,9-trimethyl-9H-fluorene was reacted completely. The reaction solution was filtered with basic alumina and MgSO₄, washed with toluene, solvents were removed through rotary evaporation and the resultant was subjected to column chromatography (PE: toluene=10:1 to 5:1) to obtain the product N-([1,1′-biphenyl]-3-yl)-2,9,9-trimethyl-9H-fluoren-3-amine (13.1 g with a yield of 79%).

Step 6:

Pd(OAc)₂ (60 mg, 0.25 mmol) and t-Bu₃PH.BF₄ (145 mg, 0.5 mmol) were put into a 100 mL three-neck flask, and xylene (50 mL) was added. The solution was purged with N₂ for 20 min until the color no longer changed, and 1,6-dibromopyrene (1.8 g, 5 mmol), N-([1,1′-biphenyl]-3-yl)-2,9,9-trimethyl-9H-fluoren-3-amine (5.625 g, 15 mmol), and sodium tert-butoxide (2.0 g, 20 mmol) were sequentially added. N₂ was continued to be introduced for 10 min and the system was heated to 80° C. until the raw materials were reacted completely.

After the reaction was finished, the reaction solution was purified through column chromatography to obtain the product, compound 339 (1 g with a yield of 21%). The product was confirmed as the target product with a molecular weight of 948.4.

Synthesis Example 2: Synthesis of Compound 347

Step 1:

Pd₂(dba)₃ (2.05 g, 2.24 mmol) and BINAP (2.98 g, 4.48 mmol) were put into a 500 mL three-neck flask, and toluene (200 mL) was added. The solution was purged with N₂ for 20 min until the color no longer changed, and 3-bromo-2,9,9-trimethyl-9H-fluorene (12.6 g, 44 mmol), 4-methyl-[1,1′-biphenyl]-3-amine (11.5 g, 66 mmol), and sodium tert-butoxide (12.86 g, 134 mmol) were sequentially added. N₂ was continued to be introduced for 10 min and the system was heated to 110° C. until 3-bromo-2,9,9-trimethyl-9H-fluorene was reacted completely. Column chromatography (PE: toluene=10:1 to 5:1) was performed to obtain the product, 2,9,9-trimethyl-N-(4-methyl-[1,1′-biphenyl]-3-yl)-9H-fluoren-3-amine (15 g with a yield of 88%).

Step 2:

Pd(OAc)₂ (60 mg, 0.25 mmol) and t-Bu₃PH.BF₄ (145 mg, 0.5 mmol) were put into a 100 mL three-neck flask, and xylene (50 mL) was added. The solution was purged with N₂ for 20 min until the color no longer changed, and 1,6-dibromopyrene (1.8 g, 5 mmol), 2,9,9-trimethyl-N-(4-methyl-[1,1′-biphenyl]-3-yl)-9H-fluoren-3-amine (5.835 g, 15 mmol), and sodium tert-butoxide (2.0 g, 20 mmol) were sequentially added. N₂ was continued to be introduced for 10 min and the system was heated to 80° C. until the raw materials were reacted completely. After the reaction was finished, the reaction solution was separated through column chromatography to obtain the product, compound 347 (1.9 g with a yield of 38.9%). The product was confirmed as the target product with a molecular weight of 976.5.

Synthesis Example 3: Synthesis of Compound 73

Step 1:

Pd(OAc)₂ (462 mg, 2.06 mmol), S-phos (1.69 g, 4.12 mmol), methylboronic acid (4.93 g, 82.34 mmol), 3-bromo-9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (15 g, 41.17 mmol), and potassium carbonate (11.38 g, 82.34 mmol) were put into a 500 mL two-neck flask, and 1,4-dioxane (150 mL) and water (50 mL) were added. The solution was purged with N₂ for 10 min, and then under nitrogen protection, the reaction system was heated to 100° C. until the raw materials were reacted completely. After the reaction was finished, the reaction was cooled to room temperature. Most of the solvents were removed through rotary evaporation under reduced pressure, and the resultant was extracted with dichloromethane and washed twice with water. The organic phases were combined, dried with anhydrous sodium sulfate, subjected to column chromatography (toluene: PE=1:10 to 1:5) and recrystallized to obtain a compound 3,9,9-trimethyl-N-phenyl-9H-fluoren-2-amine (8.5 g with a yield of 69%).

Step 2:

Pd(OAc)₂ (37 mg, 0.17 mmol) and t-Bu₃PH.BF₄ (97 mg, 0.33 mmol) were put into a 250 mL two-neck flask, and xylene (70 mL) was added. The solution was purged with N₂ for 10 min until the color no longer changed, and 1,6-dibromopyrene (2 g, 5.55 mmol), the compound 3,9,9-trimethyl-N-phenyl-9H-fluoren-2-amine (3.66 g, 12.21 mmol), and sodium tert-butoxide (2.67 g, 27.75 mmol) were sequentially added. N₂ was continued to be introduced for 10 min and the system was heated to 90° C. until the raw materials were reacted completely. After the reaction was finished, column chromatography was performed to obtain the product, compound 73 (2.7 g with a yield of 61%). The product was confirmed as the target product with a molecular weight of 796.4.

Synthesis Example 4: Synthesis of Compound 743

Step 1:

Under nitrogen protection and at room temperature, chrysene (8.2 g, 35.92 mmol) was added into 1,2-dichloroethane (DCE, 400 mL) and stirred for 10 min (not fully dissolved), and then bromine (12.6 g, 79.02 mmol in 50 mL of DCE) was added dropwise. After the dropwise addition, the reaction solution was heated to 85° C. for 16 h. The reaction was monitored by TLC. After the reaction was finished, the reaction solution was concentrated. Methanol was added, and solids were precipitated. The solids were filtered and collected, and recrystallized twice from toluene. The solids were refluxed in THF overnight, filtered, and collected to obtain 6,12-dibromochrysene (7 g, 50%) as a white solid.

Step 2:

Under nitrogen protection and at room temperature, cyclic Pd(OAc)₂ (35.0 mg, 0.16 mmol) was added into xylene (100 mL) and stirred for 10 min, and then t-Bu₃PH.BF₄ (90.0 mg, 0.31 mmol) was added and stirred for 20 min. 6,12-Dibromochrysene (2.0 g, 5.18 mmol) was added into the reaction system and stirred for 5 min Then 3,9,9-trimethyl-N-phenyl-9H-fluoren-2-amine (3.9 g, 12.95 mmol) was added into the reaction solution and stirred for 5 min. Then sodium tert-butoxide (2.0 g, 20.72 mmol) was added, and the reaction solution was heated to 95° C. for 3 h. The reaction was monitored by TLC. After the reaction was finished, column chromatography was performed to obtain the product, compound 743 (2.6 g with a yield of 63%). The product was confirmed as the target product with a molecular weight of 822.4.

Synthesis Example 5: Synthesis of Compound 466

Step 1:

Under nitrogen protection, (2-(methoxycarbonyl)phenyl)boronic acid (59.4 g, 330 mmol), 2-bromo-1-fluoro-4-iodobenzene (90 g, 300 mmol), tetra(triphenylphosphine)palladium (5 g, 4 mmol), potassium phosphate (127 g, 600 mmol), and DMF (1 L) were sequentially added. The reaction was heated to 100° C. and reacted overnight. The organic phases were removed through rotary evaporation, and the crude product was dissolved in DCM and separated through column chromatography to obtain the product, methyl 3′-bromo-4′-fluoro-[1,1′-biphenyl]-2-carboxylate (31 g with a yield of 33.3%).

Step 2:

Methyl 3′-bromo-4′-fluoro-[1,1′-biphenyl]-2-carboxylate (31 g, 100 mmol) was dissolved in 500 mL of THF and cooled to 0° C. under nitrogen protection. MeMgBr (250 mL, 250 mmol) was slowly dropwise added. The reaction mixture was slowly heated to 60° C. and refluxed for 3 h. After the reaction was cooled to room temperature, water was added to quench the reaction. The aqueous phase was extracted three times with DCM. The organic phases were combined and subjected to rotary evaporation to dryness. 200 mL of acetic acid and a catalytic amount of sulfuric acid were added, heated to 120° C., and reacted for 3 h. Water was added to quench the reaction, and the reaction solution was extracted with DCM to obtain the crude product and separated through column chromatography to finally obtain the product, 3-bromo-2-fluoro-9,9-dimethyl-9H-fluorene (26.19 g with a yield of 90%).

Step 3:

Pd₂(dba)₃ (2.05 g, 2.24 mmol) and BINAP (2.98 g, 4.48 mmol) were put into a 500 mL three-neck flask, and toluene (200 mL) was added. The solution was purged with N₂ for 20 min until the color no longer changed, and 3-bromo-2-fluoro-9,9-dimethyl-9H-fluorene (12.8 g, 44 mmol), 4-methyl-[1,1′-biphenyl]-3-amine (11.5 g, 66 mmol), and sodium tert-butoxide (12.86 g, 134 mmol) were sequentially added. N₂ was continued to be introduced for 10 min and the system was heated to 110° C. until 3-bromo-2-fluoro-9,9-dimethyl-9H-fluorene was reacted completely. The resultant was purified through column chromatography (PE: toluene=10:1 to 5:1) to obtain the product, 2-fluoro-9,9-dimethyl-N-(4-methyl-[1,1′-biphenyl]-3-yl)-9H-fluoren-3-amine (10 g with a yield of 58%).

Step 4:

Pd(OAc)₂ (60 mg, 0.25 mmol) and t-Bu₃PH.BF₄ (145 mg, 0.5 mmol) were put into a 100 mL three-neck flask, and xylene (50 mL) was added. The solution was purged with N₂ for 20 min until the color no longer changed, and 1,6-dibromopyrene (1.8 g, 5 mmol), 2-fluoro-9,9-dimethyl-N-(4-methyl-[1,1′-biphenyl]-3-yl)-9H-fluoren-3-amine (5.9 g, 15 mmol), and sodium tert-butoxide (2.0 g, 20 mmol) were sequentially added. N₂ was continued to be introduced for 10 min and the system was heated to 80° C. until the raw materials were reacted completely. After the reaction was finished, the reaction solution was purified through column chromatography to obtain the product, compound 466 (1 g with a yield of 20%). The product was confirmed as the target product with a molecular weight of 984.4.

Synthesis Example 6: Synthesis of Compound 419

Step 1:

Under nitrogen protection, the compound 2,9,9-trimethyl-N-(4-methyl-[1,1′-biphenyl]-3-yl)-9H-fluoren-3-amine (5.835 g, 15 mmol) was added into a dry 100 mL three-neck flask, and 20 mL of deuterated DMSO and potassium tert-butoxide (2.24 g, 20 mmol) were added, heated to 80° C., and reacted for 4 h. The reaction solution was cooled to room temperature and separated through column chromatography to finally obtain an intermediate, 2,9,9-trimethyl-N-(4-methyl(d3)-[1,1′-biphenyl]-3-yl)-9H-fluoren-3-amine (5.44 g with a yield of 93%).

Step 2:

Pd(OAc)₂ (60 mg, 0.25 mmol) and t-Bu₃PH.BF₄ (145 mg, 0.5 mmol) were put into a 100 mL three-neck flask, and xylene (50 mL) was added. The solution was purged with N₂ for 20 min until the color no longer changed, and 1,6-dibromopyrene (1.8 g, 5 mmol), 2,9,9-trimethyl-N-(4-methyl(d3)-[1,1′-biphenyl]-3-yl)-9H-fluoren-3-amine (5.44 g, 14 mmol), and sodium tert-butoxide (2.0 g, 20 mmol) were sequentially added. N₂ was continued to be introduced for 10 min and the system was heated to 80° C. until the raw materials were reacted completely. After the reaction was finished, the reaction solution was separated through column chromatography to obtain the product, compound 419 (1.9 g with a yield of 38.9%). The product was confirmed as the target product with a molecular weight of 988.5.

Synthesis Example 7: Synthesis of Compound 422

Step 1:

Under nitrogen protection, 3-bromo-2-iodo-9,9-dimethyl-9H-fluorene (24 g, 0.06 mol) was dissolved in 1 L of anhydrous tetrahydrofuran and cooled to −78° C. Isopropylmagnesium chloride (1.3M, 0.066 mol) was slowly added and reacted at low temperature for 1 h. Deuterated propanone (10.44 g, 0.18 mol) was added, slowly warmed to room temperature, and reacted overnight. After the reaction was finished, water was added to quench the reaction. The aqueous phase was extracted three times with DCM. The organic phases were combined, filtered through Celite, and the solvent was removed through rotary evaporation under reduced pressure, and then purified through column chromatography to obtain a tertiary alcohol intermediate. The intermediate was dissolved in 500 mL of dichloromethane. Triethylsilane (17.4 g, 0.15 mmol) was added at room temperature and stirred for half an hour. Trifluoroacetic acid (11.4 g, 0.1 mmol) was slowly dropwise added and stirred overnight at room temperature. Column chromatography was performed to obtain the product, 3-bromo-9,9-dimethyl-2-(propyl-2-yl-1,1,1,3,3,3-d6)-9H-fluorene (15.7 g with a yield of 67%).

Step 2:

Under nitrogen protection, 3-bromo-9,9-dimethyl-2-(propyl-2-yl-1,1,1,3,3,3-d6)-9H-fluorene (16 g, 50 mmol), benzophenone imine (10 g, 55 mmol), Pd(OAc)₂ (567 mg, 2.5 mmol), dppf (2.8 g, 5 mmol), and sodium tert-butoxide (10 g, 101 mmol) were sequentially added into a dry 500 mL three-neck flask, and xylene (125 mL) was added into the reaction flask which was purged with nitrogen for 5 min The system was heated to 100° C. until the raw materials were reacted completely. The reaction solution was purified through column chromatography to obtain an intermediate. The intermediate was dissolved in 100 mL of THE HCl (30 mL) was added at room temperature and stirred overnight at room temperature, and column chromatography was performed to obtain the product, 9,9-dimethyl-2-(propyl-2-yl-1,1,1,3,3,3-d6)-9H-fluoren-3-amine (10 g with a yield of 77%).

Step 3:

Under nitrogen protection, 3-bromo-4-iodo-1,1′-biphenyl (24 g, 0.06 mol) was dissolved in 1 L of anhydrous tetrahydrofuran and cooled to −78° C. Isopropylmagnesium chloride (1.3M, 0.066 mol) was slowly added and reacted at low temperature for 1 h. Propanone (10.44 g, 0.18 mol) was added, slowly warmed to room temperature, and reacted overnight. After the reaction was finished, water was added to quench the reaction. The aqueous phase was extracted three times with DCM. The organic phases were combined and filtered through Celite. After silica gel powder was added, samples were dry-mixed and subjected to column chromatography to obtain a tertiary alcohol intermediate. The intermediate was dissolved in 500 mL of dichloromethane. Triethylsilane (17.4 g, 0.15 mmol) was added at room temperature and stirred for half an hour. Trifluoroacetic acid (11.4 g, 0.1 mmol) was slowly dropwise added and stirred overnight at room temperature. Column chromatography was performed to obtain the product, 3-bromo-4-(propyl-2-yl-1,1,1,3,3,3-d6)-1,1′-biphenyl (15.7 g with a yield of 67%).

Step 4:

Under nitrogen protection, 3-bromo-9,9-dimethyl-2-(propyl-2-yl-1,1,1,3,3,3-d6)-9H-fluorene (8 g, 31.1 mmol), 3-bromo-4-(propyl-2-yl-1,1,1,3,3,3-d6)-1,1′-biphenyl (6.7 g, 23.8 mmol), Pd(OAc)₂ (530 mg, 2.4 mmol), t-Bu₃PHBF₄ (0.96 g, 4.76 mmol), and sodium tert-butoxide (5 g, 52.4 mmol) were sequentially added into a dry 500 mL three-neck flask, and xylene (125 mL) was added into the reaction flask , then the reaction system was purged with nitrogen for 5 min. The system was heated to 100° C. until the raw materials were reacted completely. The reaction solution was diluted with toluene, filtered through Celite, distilled under reduced pressure, and purified through column chromatography to obtain a compound, 9,9-dimethyl-2-(propyl-2-yl-1,1,1,3,3,3-d6)-N-4-(propyl-2-yl-1,1,1,3,3,3-d6)-[1,1′-biphenyl]-3-yl)-9H-fluoren-3-amine (8 g, 17.5 mmol, 74%).

Step 5:

Under nitrogen protection, 9,9-dimethyl-2-(propyl-2-yl-1,1,1,3,3,3-d6)-N-4-[(propyl-2-yl-1,1,1,3,3,3-d6)-1,1′-biphenyl]-3-yl)-9H-fluoren-3-amine (7.5 g, 16.3 mmol) and potassium tert-butoxide (2.8 g, 24.5 mmol) were sequentially added into a dry 100 mL three-neck flask, and DMSO (40 mL) was added into the reaction flask, then the reaction system was purged with nitrogen for 5 min. The system was heated to 140 □ until the raw materials were reacted completely. Water was added to quench the reaction. The aqueous phase was extracted three times with DCM. The organic phases were combined, filtered through Celite, and purified through column chromatography to obtain a compound, 9,9-dimethyl-2-(propyl-2-yl-d7)-N-4-(propyl-2-yl-1,1,1,3,3,3-d6)-[1,1′-biphenyl]-3-yl)-9H-fluoren-3-amine (4 g with a yield of 54%).

Step 6:

Compound 422

Under nitrogen protection and at room temperature, 9,9-dimethyl-2-(propyl-2-yl-d7)-N-4-(propyl-2-yl-1,1,1,3,3,3-d6)-[1,1′-biphenyl]-3-yl)-9H-fluoren-3-amine (3.6 g, 7.8 mmol) was dissolved in 20 mL of THF and cooled to −78° C., and n-hexyl lithium (7 mmol) was slowly dropwise added. The reaction mixture was warmed to room temperature and stirred for 30 min Additionally, xylene (20 mL), 1,6-dibromopyrene (1.1 g, 3.1 mmol), Pd(OAc)₂ (37.0 mg, 0.17 mmol), and t-Bu₃P (0.33 mmol) were added into another flask under nitrogen protection. The prepared amino-lithium solution was slowly dropwise added into the reaction system under nitrogen protection, warmed to 90° C., and stirred for 3 h. After the reaction was finished, the reaction solution was purified through column chromatography to obtain the product, compound 422 (1.2 g with a yield of 35%). The product was confirmed as the target product with a molecular weight of 1116.8.

Synthesis Example 8: Synthesis of Compound 2333

Step 1:

At room temperature and under nitrogen protection, Pd₂(dba)₃ (910 mg, 0.99 mmol), BINAP (1.18 g, 1.99 mmol), 6-fluoro-4-methyl-[1,1′-biphenyl]-3-amine (6.03 g, 30 mmol), 3-bromo-2,9,9-trimethyl-9H-fluorene (5.6 g, 20 mmol), and t-BuONa (3.8 g, 39.8 mmol) were added into toluene (200 mL), and the system was heated to 120° C. for 2 h. After the reaction was finished, the reaction solution was purified through column chromatography to obtain a compound 2,9,9-trimethyl-N-(6-fluoro-4-methyl-[1,1′-biphenyl]-3-yl)-9H-fluoren-3-amine (7.8 g with a yield of 95%).

Step 2:

At room temperature and under nitrogen protection, 1,6-dibromopyrene (2.2 g, 6.1 mmol), 2,9,9-trimethyl-N-(6-fluoro-4-methyl-[1,1′-biphenyl]-3-yl)-9H-fluoren-3-amine (5.52 g, 16 mmol), Pd(OAc)₂ (68 mg, 0.3 mmol), t-Bu₃PH⁺BF₄ ⁻ (174 mg, 0.6 mmol), and t-BuONa (1.3 g, 14 mmol) were added into xylene (30 mL), and the system was heated to 95 □. After the reaction was finished, the reaction solution was separated through column chromatography to obtain the product, compound 2333 (1.95 g, 1.9 mmol, with a yield of 37%). The product was confirmed as the target product with a molecular weight of 1012.5.

Synthesis Example 9: Synthesis of Compound 2334

Step 1:

At room temperature and under nitrogen protection, Pd₂(dba)₃ (910 mg, 0.99 mmol), BINAP (1.18 g, 1.99 mmol), 3-bromo-2,9,9-trimethyl-9H-fluorene (8.6 g, 30 mmol), 5-fluoro-[1,1′-biphenyl]-3-amine (3.75 g, 19.9 mmol), and t-BuONa (3.8 g, 39.8 mmol) were added into toluene (200 mL), and the system was heated to 120° C. for 2h. After the reaction was finished, the reaction solution was purified through column chromatography to obtain a compound 2,9,9-trimethyl-N-(3-fluoro-[1,1′-biphenyl]-3-yl)-9H-fluoren-3-amine (6.29 g with a yield of 53%).

Step 2:

At room temperature and under nitrogen protection, 1,6-dibromopyrene (2.2 g, 6.1 mmol), 2,9,9-trimethyl-N-(3-fluoro-[1,1′-biphenyl]-3-yl)-9H-fluoren-3-amine (6.29 g, 16 mmol), Pd(OAc)₂ (68 mg, 0.3 mmol), tBu₃PHBF₄ (174 mg, 0.6 mmol), and t-BuONa (1.3 g, 14 mmol) were added into xylene (30 mL), and the system was heated to 95 □. After the reaction was finished, the reaction solution was separated through column chromatography to obtain the product, compound 2334 (1.8 g, 2 mmol, with a yield of 33%). The product was confirmed as the target product with a molecular weight of 984.4.

Synthesis Example 10: Synthesis of Compound 506

Step 1:

At room temperature and under nitrogen protection, Pd(OAc)₂ (0.2 g, 1 mmol), 3-chloro-2,9,9-trimethyl-5-phenyl-9H-fluorene (3.3 g, 10.3 mmol), 4-methyl-[1,1′-biphenyl]-3-amine (3.8 g, 20.7 mmol), t-Bu₃P (4 mL, 2 mmol), and t-BuONa (3 g, 31 mmol) were added into xylene (40 mL), and the system was heated to 140 □ and reacted overnight. The reaction solution was filtered, washed with toluene, solvents were removed through rotary evaporation and the resultant was subjected to column chromatography (PE/EA=20/1) to obtain a crude product. The crude product was recrystallized to obtain a compound 2,9,9-trimethyl-N-(4-methyl-[1,1′-biphenyl]-3-yl)-5-phenyl-9H-fluoren-3-amine (3.8 g with a yield of 79%).

Step 2:

At room temperature and under nitrogen protection, 1,6-dibromopyrene (1 g, 2.89 mmol), 2,9,9-trimethyl-N-(4-methyl-[1,1′-biphenyl]-3-yl)-5-phenyl-9H-fluoren-3-amine (3 g, 6.36 mmol), Pd(OAc)₂ (31 mg, 0.14 mmol), t-Bu₃PHBF₄ (81.2 mg, 0.28 mmol), and t-BuONa (1.4 g, 14.5 mmol) were added into xylene (20 mL), and the system was heated to 100 □ until the reaction was finished. After the reaction was finished, the reaction solution was purified through column chromatography to obtain the product, compound 506 (1.2 g with a yield of 36%). The product was confirmed as the target product with a molecular weight of 1128.5.

Synthesis Example 11: Synthesis of Compound 609

Step 1:

At room temperature and under nitrogen protection, Pd(OAc)₂ (0.2 g, 1 mmol), 3-chloro-4,9,9-trimethyl-9H-fluorene (6 g, 24.9 mmol), 4-methyl-[1,1′-biphenyl]-3-amine (9.3 g, 49.8 mmol), t-Bu₃P (4 mL, 2 mmol), and t-BuONa (7.1 g, 74.7 mmol) were added into xylene (40 mL), and the system was heated to 140 □ and reacted overnight. The reaction solution was filtered with basic alumina and MgSO₄, washed with toluene, solvents were removed through rotary evaporation and the resultant was subjected to column chromatography (PE/EA=20/1) to obtain a crude product. The crude product was recrystallized from PE to obtain a compound 4,9,9-trimethyl-N-(4-methyl-[1,1′-biphenyl]-3-yl)-9H-fluoren-3-amine (7 g with a yield of 72%).

Step 2:

At room temperature and under nitrogen protection, 1,6-dibromopyrene (2 g, 5.56 mmol), 4,9,9-trimethyl-N-(4-methyl-[1,1′-biphenyl]-3-yl)-9H-fluoren-3-amine (4.4 g, 12.2 mmol), Pd(OAc)₂ (31 mg, 0.14 mmol), t-Bu₃PHBF₄ (81.2 mg, 0.28 mmol), and t-BuONa (2.1 g, 22.2 mmol) were added into xylene (20 mL), and the system was heated to 100 □ until the reaction was finished. After the reaction was finished, the reaction solution was separated through column chromatography to obtain the product, compound 609 (1.3 g with a yield of 24%). The product was confirmed as the target product with a molecular weight of 976.5.

Synthesis Example 12: Synthesis of Compound 2350

Step 1:

At room temperature and under nitrogen protection, 1,6-dibromo-3,8-diisopropylpyrene (2 g, 4.5 mmol), 2,9,9-trimethyl-N-(4-methyl-[1,1′-biphenyl]-3-yl)-9H-fluoren-3-amine (4 g, 10.35 mmol), Pd(OAc)₂ (50 mg, 0.225 mmol), t-Bu₃PHBF₄ (130 mg, 0.45 mmol), and t-BuONa (1 g, 10.23 mmol) were added into xylene (25 mL), and the system was heated to 95 □. The reaction was monitored by TLC until it was finished. After the reaction was finished, the reaction was purified through column chromatography to obtain the product, compound 2350 (2.5 g with a yield of 50%). The product was confirmed as the target product with a molecular weight of 1060.6.

Synthesis Example 13: Synthesis of Compound 505

Step 1:

At room temperature and under nitrogen protection, Pd(OAc)₂ (0.2 g, 1 mmol), 3-chloro-5-cyclohexyl-2,9,9-trimethyl-9H-fluorene (3 g, 9.2 mmol), 4-methyl-[1,1′-biphenyl]-3-amine (3.3 g, 18.5 mmol), t-Bu₃P (4 mL, 2 mmol), and t-BuONa (2.7 g, 27.7 mmol) were added into xylene (40 mL), and the system was heated to 140 □ and reacted overnight. The reaction solution was filtered with basic alumina and MgSO₄, washed with toluene, solvents were removed through rotary evaporation and the resultant was subjected to column chromatography (PE/EA=20/1) to obtain a crude product. The crude product was crystallized from PE to obtain a compound 5-cyclohexyl-2,9,9-trimethyl-N-(4-methyl-[1,1′-biphenyl]-3-yl)-9H-fluoren-3-amine (3.2 g with a yield of 75%).

Step 2:

At room temperature and under nitrogen protection, 1,6-dibromopyrene (1 g, 2.89 mmol), 5-cyclohexyl-2,9,9-trimethyl-N-(4-methyl-[1,1′-biphenyl]-3-yl)-9H-fluoren-3-amine (3 g, 6.36 mmol), Pd(OAc)₂ (31 mg, 0.14 mmol), t-Bu₃PHBF₄ (81.2 mg, 0.28 mmol), and t-BuONa (1.4 g, 14.5 mmol) were added into xylene (20 mL), and the system was heated to 100 □ until the reaction was finished. After the reaction was finished, the reaction solution was separated through column chromatography to obtain the product, compound 505 (1.3 g with a yield of 39%). The product was confirmed as the target product with a molecular weight of 1140.6.

Synthesis Example 14: Synthesis of Compound 508

Step 1:

At room temperature and under nitrogen protection, Pd₂(dba)₃ (0.4 g, 0.45 mmol) and BINAP (0.56 g, 0.90 mmol) were added into xylene (100 mL). The solution was purged with N₂ for 20 min, and 7-chloro-6,9,9-trimethyl-9H-fluoren-4-cyano (4.0 g, 14.98 mmol), 4-methyl-[1,1′-biphenyl]-3-amine (5.0 g, 26.96 mmol), and sodium tert-butoxide (3.6 g, 37.45 mmol) were sequentially added. N₂ was continued to be introduced for 10 min and the system was heated to 140 □ for 18 h. The reaction solution was filtered with basic alumina and MgSO₄, washed with toluene, solvents were removed through rotary evaporation and the resultant was subjected to column chromatography (PE:EA=20: 1) to obtain a crude product. The crude product was crystallized from petroleum ether to obtain 6,9,9-trimethyl-7-((4-methyl-[1,1′-biphenyl]-3-yeamino)-9H-fluoren-4-cyano (4.0 g with a yield of 64%) as a white solid.

Step 2:

At room temperature and under nitrogen protection, Pd₂(dba)₃ (356 mg, 0.39 mmol) and t-Bu₃PHBF₄ (225 mg, 0.78 mmol) were added into xylene (20 mL). The solution was purged with N₂ for 20 min, and 1,6-dibromopyrene (1.4 g, 3.89 mmol), 6,9,9-trimethyl-7-((4-methyl-[1,1′-biphenyl]-3-yl)amino)-9H-fluoren-4-cyano (3.7 g, 8.94 mmol), and sodium tert-butoxide (0.9 g, 9.72 mmol) were sequentially added. N₂ was continued to be introduced for 10 min and the system was heated to 100 □ until the reaction was finished. The reaction solution was filtered with basic alumina and MgSO₄, washed with toluene, solvents were removed through rotary evaporation and the resultant was subjected to column chromatography (PE:toluene=10:1 to 1:5) to obtain compound 508 (0.75 g with a yield of 19%) as a yellow-green solid. The product was confirmed as the target product with a molecular weight of 1026.5.

Synthesis Example 15: Synthesis of Compound 349

Step 1:

Under nitrogen protection, 3-bromo-2-iodo-9,9-dimethyl-9H-fluorene (24 g, 0.06 mol) was dissolved in 1 L of anhydrous tetrahydrofuran and cooled to −78° C. Isopropylmagnesium chloride (1.3M, 0.066 mol) was slowly added and reacted at low temperature for 1 h. Propanone (10.44 g, 0.18 mol) was added, slowly warmed to room temperature, and reacted overnight. After the reaction was finished, water was added to quench the reaction. The aqueous phase was extracted three times with DCM. The organic phases were combined, filtered through Celite, and subjected to column chromatography to obtain a tertiary alcohol intermediate. The intermediate was dissolved in 500 mL of dichloromethane. Triethylsilane (17.4 g, 0.15 mmol) was added at room temperature and stirred for half an hour. Trifluoroacetic acid (11.4 g, 0.1 mmol) was slowly dropwise added and stirred overnight at room temperature. Column chromatography was performed to obtain the product, 3-bromo-9,9-dimethyl-2-isopropyl-9H-fluorene (15.7 g with a yield of 67%).

Step 2:

Under nitrogen protection, 3-bromo-9,9-dimethyl-2-isopropyl-9H-fluorene (8 g, 25.6 mmol), 4-isopropyl-[1,1′-biphenyl]-3-amine (3 g, 14.22 mmol), Pd₂(dba)₃ (586 mg, 0.64 mmol), S-Phos (1.05 g, 2.56 mmol), and sodium tert-butoxide (3 g, 31.3 mmol) were sequentially added into a dry 500 mL three-neck flask, and xylene (125 mL) was added into the reaction flask which was purged with nitrogen for 5 min. The system was heated to 100° C. until the raw materials were reacted completely. The reaction solution was diluted with toluene and filtered. The filtrate was distilled under reduced pressure and separated through column chromatography to obtain a product 2-isopropyl-N-(4-isopropyl-[1,1′-biphenyl]-3-yl)-9,9-dimethyl-9H-fluoren-3-amine (9.1 g with a yield of 80%) as a light yellow oil.

Step 3:

Under nitrogen protection and at room temperature, 2-isopropyl-N-(4-isopropyl-[1,1′-biphenyl]-3-yl)-9,9-dimethyl-9H-fluoren-3-amine (8.9 g, 20 mmol) was dissolved in 40 mL of THF and cooled to −78 □, and n-hexyl lithium (20 mmol) was slowly dropwise added. The reaction mixture was warmed to room temperature and stirred for 30 min. Additionally, xylene (40 mL), 1,6-dibromopyrene (2.88 g, 8 mmol), Pd(OAc)₂ (37.0 mg, 0.17 mmol), and t-Bu₃P (0.33 mmol) were added into another flask under nitrogen protection. The prepared amino-lithium solution was slowly dropwise added into the reaction system under nitrogen protection, warmed to 90° C., and stirred for 3 h. After the reaction was finished, the reaction was purified through column chromatography to obtain the product, compound 349 (2.8 g with a yield of 33%). The product was confirmed as the target product with a molecular weight of 1088.6.

Synthesis Example 16: Synthesis of Compound 2335

Step 1:

At room temperature and under nitrogen protection, Pd₂(dba)₃ (1.7 g, 1.88 mmol) and BINAP (2.3 g, 3.76 mmol) were added into xylene (300 mL). The solution was purged with N₂ for 20 min, and 3-bromo-2,9,9-trimethyl-9H-fluorene (18.0 g, 62.67 mmol), 2′-fluoro-4-methyl-[1,1′-biphenyl]-3-amine (13.0 g, 64.6 mmol), and sodium tert-butoxide (15.0 g, 156.8 mmol) were sequentially added. N₂ was continued to be introduced for 10 min and the system was heated to 140 □ for 4 h. The reaction solution was filtered with basic alumina and MgSO₄, washed with toluene, solvents were removed through rotary evaporation and the resultant was subjected to column chromatography (PE:toluene=50:1) to obtain a compound N-(2′-fluoro-4-methyl-[1,1′-biphenyl]-3-yl)-2,9,9-trimethyl-9H-fluoren-3-amine (6.0 g with a yield of 23%).

Step 2:

At room temperature and under nitrogen protection, Pd(OAc)₂ (65 mg, 0.29 mmol) and t-Bu₃PHBF₄ (169 mg, 0.58 mmol) were added into xylene (30 mL). The solution was purged with N₂ for 20 min, and 1,6-dibromopyrene (2.1 g, 5.89 mmol), N-(2′-fluoro-4-methyl-[1,1′-biphenyl]-3-yl)-2,9,9-trimethyl-9H-fluoren-3-amine (6.0 g, 14.72 mmol), and sodium tert-butoxide (1.7 g, 17.5 mmol) were sequentially added. N₂ was continued to be introduced for 10 min and the system was heated to 100° C. until the reaction was finished. After the reaction was finished, the reaction solution was purified through column chromatography to obtain the product, compound 2335 (1.0 g, 0.98 mmol, with a yield of 17%). The product was confirmed as the target product with a molecular weight of 1012.5.

Synthesis Example 17: Synthesis of Compound 2336

Step 1:

At room temperature and under nitrogen protection, Pd(OAc)₂ (0.2 g, 1 mmol), 4′-t-butyl-4-methyl-[1,1′-biphenyl]-3-amine (8 g, 33.5 mmol), 3-chloro-2,9,9-trimethyl-9H-fluorene (6.8 g, 27.9 mmol), t-Bu₃P (4 mL, 2 mmol), and t-BuONa (8.3 g, 86.9 mmol) were added into xylene (100 mL), and the system was heated to 140 □ and reacted overnight. The reaction solution was filtered with basic alumina and MgSO₄, washed with toluene, solvents were removed through rotary evaporation and the resultant was subjected to column chromatography (PE/EA=20/1) to obtain a crude product. The crude product was crystallized from PE to obtain a compound 2,9,9-trimethyl-N-(4′-t-butyl-4-methyl-[1,1′-biphenyl]-3-yl)-9H-fluoren-3-amine (10.7 g with a yield of 86%).

Step 2:

At room temperature and under nitrogen protection, 2,9,9-trimethyl-N-(4′-t-butyl-4-methyl-[1,1′-biphenyl]-3-yl)-9H-fluoren-3-amine (2.4 g, 5.38 mmol), 1,6-dibromopyrene (0.77 g, 2.15 mmol), Pd(OAc)₂ (63 mg, 0.28 mmol), t-Bu₃PHBF₄ (162 mg, 0.56 mmol), and t-BuONa (2.13 g, 22.22 mmol) were added into xylene (20 mL), and the system was heated to 100 □ until the reaction was finished. After the reaction was finished, column chromatography was performed to obtain the product, compound 2336 (0.8 g with a yield of 34%). The product was confirmed as the target product with a molecular weight of 1088.6.

Synthesis Example 18: Synthesis of Compound 2337

Step 1:

At room temperature and under nitrogen protection, palladium acetate (234.0 mg, 1.1 mmol) and BINAP (1.3 g, 2.1 mmol) were added into toluene (100 mL). The solution was purged with N₂ for 20 min, and 3-bromo-2,9,9-trimethyl-9H-fluorene (10.0 g, 34.9 mmol), 4-fluoro-[1,1′-biphenyl]-3-amine (6.7 g, 35.66 mmol), and sodium tert-butoxide (8.4 g, 87.4 mmol) were sequentially added. N₂ was continued to be introduced for 10 min and the system was heated to 110 □ for 4 h. After the reaction was finished, the solvent was removed through rotary evaporation under reduced pressure, and the resultant was subjected to column chromatography to obtain a compound N-(4-fluoro-[1,1′-biphenyl]-3-yl)-2,9,9-trimethyl-9H-fluoren-3-amine (9.0 g, 22.9 mmol, with a yield of 66%).

Step 2:

At room temperature and under nitrogen protection, Pd(OAc)₂ (47.0 mg, 0.24 mmol) and t-Bu₃PHBF₄ (121.0 mg, 0.42 mmol) were added into xylene (50 mL). The solution was purged with N₂ for 20 min, and 1,6-dibromopyrene (2.5 g, 6.94 mmol), N-(4-fluoro-[1,1′-biphenyl]-3-yl)-2,9,9-trimethyl-9H-fluoren-3-amine (6.8 g, 17.36 mmol), and sodium tert-butoxide (1.7 g, 17.36 mmol) were sequentially added. N₂ was continued to be introduced for 10 min and the system was heated to 100 □ until the reaction was finished. The solvent was removed through rotary evaporation under reduced pressure, and the resultant was purified through column chromatography to obtain the product, compound 2337 (4.0 g, 4.07 mmol, with a yield of 59%). The product was confirmed as the target product with a molecular weight of 984.4.

Comparative Synthesis Example 1: Synthesis of Comparative Compound A

Step 1:

Pd₂(dba)₃ (587 mg, 1.28 mmol) and BINAP (1.59 g, 2.56 mmol) were added into a 500 mL three-neck flask, and xylene (130 mL) was added. The solution was purged with N₂ for 20 min until the color no longer changed, and [1,1′-biphenyl]-3-amine (5.6 g, 32.9 mmol), 3-bromo-9,9-dimethyl-fluorene (6.0 g, 21.9 mmol), and sodium tert-butoxide (5.3 g, 54.91 mmol) were sequentially added. N₂ was continued to be introduced for 10 min and the system was stirred at 110° C. until the raw materials were reacted completely. The solvent was removed through rotary evaporation under reduced pressure, and the resultant was purified through column chromatography to obtain a compound 9,9-dimethyl-N-([1,1′-biphenyl]-3-yl)-9H-fluoren-3-amine (6.5 g with a yield of 82%).

Step 2:

Pd(OAc)₂ (56 mg, 0.25 mmol) and t-Bu₃PH.BF₄ (145 mg, 0.5 mmol) were added into a 250 mL three-neck flask, and xylene (100 mL) was added. The solution was purged with N₂ for 20 min until the color no longer changed, and 1,6-dibromopyrene (2.0 g, 5.5 mmol), the compound 9,9-dimethyl-N-([1,1′-biphenyl]-3-yl)-9H-fluoren-3-amine (6.5 g, 17.9 mmol), and sodium tert-butoxide (1.6 g, 16.6 mmol) were sequentially added. N₂ was continued to be introduced for 10 min and the system was stirred at 90° C. until the raw materials were reacted completely. The solvent was removed through rotary evaporation under reduced pressure, and the resultant was purified through column chromatography to obtain the product, compound A (4.0 g with a yield of 78%). The product was confirmed as the target product with a molecular weight of 920.4.

Comparative Synthesis Example 2: Synthesis of Comparative Compound B

Step 1:

Under nitrogen protection and at room temperature, Pd₂(dba)₃ (2.1 g, 2.2 mmol) was added into toluene (200 mL) and stirred for 10 min, and then BINAP (3.0 g, 4.5 mmol) was added and stirred for 20 min. 2-Bromo-9,9-dimethyl-9H-fluorene (11.9 g, 44.1 mmol) was added into the reaction solution and stirred until it was completely dissolved. Phenylamine (6.1 g, 66.0 mmol) was added and stirred for 5 min Then sodium tert-butoxide (12.9 g, 134.0 mmol) was added, and the reaction solution was warmed to 110° C. for 3 h. After the reaction was finished, the solvent was removed through rotary evaporation under reduced pressure, and the resultant was purified through column chromatography to obtain 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (11.5 g with a yield of 93%) as a white solid.

Step 2:

Under nitrogen protection and at room temperature, Pd(OAc)₂ (60.0 mg, 0.25 mmol) was added into xylene (50 mL) and stirred for 10 min, and then t-Bu₃PH.BF₄ (145.0 mg, 0.5 mmol) was added and stirred for 20 min 1,6-Dibromopyrene (1.8 g, 5.0 mmol) was added into the reaction system and stirred until it was dissolved completely. Then 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (4.2 g, 15.0 mmol) was added into the reaction solution and stirred until it was dissolved completely. Then sodium tert-butoxide (2.0 g, 20.0 mmol) was added, and the reaction solution was warmed to 95° C. After the reaction was finished, the solvent was removed through rotary evaporation under reduced pressure, and the resultant was purified through column chromatography to obtain compound B (3.0 g with a yield of 78%). The product was confirmed as the target product with a molecular weight of 768.4.

Comparative Synthesis Example 3: Synthesis of Comparative Compound C

Pd(OAc)₂ (60 mg, 0.25 mmol) and t-Bu₃PH.BF₄ (145 mg, 0.5 mmol) were put into a 100 mL three-neck flask, and xylene (50 mL) was added. The solution was purged with N₂ for 20 min until the color no longer changed, and 6,12-dibromochrysene (1.9 g, 5 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (4.275 g, 15 mmol), and sodium tert-butoxide (2.0 g, 20 mmol) were sequentially added. N₂ was continued to be introduced for 10 min and the system was heated to 80° C. until the raw materials were reacted completely. After the reaction was finished, column chromatography was performed to obtain the product, compound C (2.8 g with a yield of 70%). The product was confirmed as the target product with a molecular weight of 794.4.

Those skilled in the art will appreciate that the above preparation methods are merely illustrative. Those skilled in the art can obtain other compound structures of the present disclosure through the improvements of the preparation methods.

Device Example

First, a glass substrate having an Indium Tin Oxide (ITO) anode with a thickness of 80 nm was cleaned and then treated with oxygen plasma and UV ozone. After the treatment, the substrate was dried in a glovebox to remove water. The substrate was mounted on a substrate holder and placed in a vacuum chamber. Organic layers specified below were sequentially deposited through vacuum thermal evaporation on the ITO anode at a rate of 0.2 to 2 Angstroms per second at a vacuum degree of about 10⁻⁸ torr. Compound HI was used as a hole injection layer (HIL). Compound HT was used as a hole transport layer (HTL). Compound EB was used as an electron blocking layer (EBL). Compound BH and the compound of the present disclosure were co-deposited as an emissive layer (EML). Compound HB was used as a hole blocking layer (HBL). On the HBL, Compound ET and 8-hydroxyquinolinolato-lithium (Liq) were co-deposited as an electron transport layer (ETL). Finally, 8-hydroxyquinolinolato-lithium (Liq) with a thickness of 1 nm was deposited as an electron injection layer, and Al with a thickness of 120 nm was deposited as a cathode. The device was transferred back to the glovebox and encapsulated with a glass lid and a moisture getter to complete the device.

Comparative Examples were prepared in the same manner except that the compound of the present disclosure was substituted with comparative compounds.

Detail structures and thicknesses of part of layers of the device are shown in tables 1 to 5. A layer using more than one material was obtained by doping different compounds in their weight proportions as described.

TABLE 1 Part device structures in Device Examples 1, 2, and 5 and Comparative Example 1 Device ID HIL HTL EBL EML HBL ETL Example 1 Compound Compound Compound Compound Compound Compound HI HT EB BH: HB (50 Å) ET:Liq (100 Å) (1200 Å) (50 Å) compound (40:60) 339 (98:2) (120 Å) (250 Å) Example 2 Compound Compound Compound Compound Compound Compound HI HT EB BH: HB (50 Å) ET:Liq (100 Å) (1200 Å) (50 Å) compound (40:60) 347 (98:2) (120 Å) (250 Å) Example 5 Compound Compound Compound Compound Compound Compound HI HT EB BH: HB (50 Å) ET:Liq (100 Å) (1200 Å) (50 Å) compound (40:60) 609 (98:2) (120 Å) (250 Å) Comparative Compound Compound Compound Compound Compound Compound Example 1 HI HT EB BH: HB (50 Å) ET:Liq (100 Å) (1200 Å) (50 Å) compound (40:60) A (98:2) (120 Å) (250 Å)

Structures of the materials used in the devices are shown as follows:

IVL of the devices was measured at different current densities and voltages. Device data, including LT97, external quantum efficiency (EQE), maximum emission wavelength (λ_(max)), full width at half maximum (FWHM), and CIE, were measured at a constant current of 10 mA/cm² in all Examples and Comparative Examples. LT97 represents the lifetime for a device to decay to 97% of initial brightness.

Discussion:

When the materials of the present disclosure are used as doping materials in the emissive layer, at the constant current of 10 mA/cm², Example 1 (with a doping proportion of 2%) exhibits EQE of 9.46%, maximum emission wavelength of 464 nm, CIE of (0.131, 0.137), LT97 of 360 h, and a half-peak width of 32.7 nm. Compared with Comparative Example 1 with the same doping proportion of 2% (which exhibits EQE of 8.06%, maximum emission wavelength of 469 nm, CIE of (0.127, 0.181), LT97 of 271 h, and a half-peak width of 37.1 nm), Example 1 has improved the EQE by 17.3% and the lifetime by 32.8%, narrowed the half-peak width by 4.4 nm, and achieved a blue-shift of 5 nm of the maximum emission wavelength. Example 2 (with a doping proportion of 2%) exhibits EQE of 9.56%, maximum emission wavelength of 461 nm, CIE of (0.134, 0.121), LT97 of 553 h, and a half-peak width of 34.3 nm. Compared with Comparative Example 1 (with a doping proportion of 2%), Example 2 has improved the lifetime by 104% and the EQE by 18.6%, narrowed the half-peak width by 2.8 nm, and achieved a blue-shift of 8 nm, thereby effectively improving blue light-emitting performance Example 5 (with a doping proportion of 2%) exhibits EQE of 9.06%, maximum emission wavelength of 460 nm, CIE of (0.136, 0.121), LT97 of 482 h, and a half-peak width of 33.8 nm. Compared with Comparative Example 1 (with a doping proportion of 2%), Example 5 has improved the lifetime by about 77.9% and the EQE by 12.4%, narrowed the half-peak width by 3.3 nm, and achieved a blue-shift of 9 nm.

It can be seen that through the introduction of an ortho-substituent into the fluorene ring, that is, the introduction of R″ in Formula 4, the compounds of the present disclosure can significantly improve the EQE and the lifetime of the devices, and decrease the CIE y value to achieve deep-blue emission of less than 0.14, thereby improving device performance significantly.

TABLE 2 Part device structures in Device Examples 3 and 4 and Comparative Examples 2 and 3 Device ID HIL HTL EBL EML HBL ETL Example 3 Compound Compound Compound Compound Compound Compound HI HT EB BH: HB (50 Å) ET:Liq (100 Å) (1200 Å) (50 Å) compound (40:60) 73 (96:4) (120 Å) (250 Å) Example 4 Compound Compound Compound Compound Compound Compound HI HT EB BH: HB (50 Å) ET:Liq (100 Å) (1200 Å) (50 Å) compound (40:60) 743 (96:4) (120 Å) (250 Å) Comparative Compound Compound Compound Compound Compound Compound Example 2 HI HT EB BH: HB (50 Å) ET:Liq (100 Å) (1200 Å) (50 Å) compound (40:60) B (96:4) (120 Å) (250 Å) Comparative Compound Compound Compound Compound Compound Compound Example 3 HI HT EB BH: HB (50 Å) ET:Liq (100 Å) (1200 Å) (50 Å) compound (40:60) A (96:4) (120 Å) (250 Å)

Structures of the new materials used in the devices are shown as follows:

Discussion:

Additionally, when the compounds of the present disclosure have a pyrene core, Example 3 (with a doping proportion of 4%) exhibits EQE of 8.38%, maximum emission wavelength of 474 nm, CIE of (0.125, 0.239), and a half-peak width of 34.9 nm. Comparative Example 2 (with a doping proportion of 4%) exhibits EQE of 7.57%, maximum emission wavelength of 481 nm, CIE of (0.132, 0.334), and a half-peak width of 38.3 nm. Compared with Comparative Example 2, Example 3 has improved the EQE by 10.7%, narrowed the half-peak width by 3.4 nm, achieved a blue-shift of 7 nm of the maximum emission wavelength, and significantly decreased the CIE y value at the same doping proportion. When the compounds of the present disclosure have a chrysene core, Example 4 (with a doping proportion of 4%) exhibits EQE of 7.20%, maximum emission wavelength of 461 nm, CIE of (0.137, 0.126), and a half-peak width of 47.4 nm. Comparative Example 3 (with a doping proportion of 4%) exhibits EQE of 6.88%, maximum emission wavelength of 466 nm, CIE of (0.134, 0.165), and a half-peak width of 47.0 nm. Compared with Comparative Example 3, Example 4 has improved the EQE by 4.6%, achieved a blue-shift of 5 nm of the maximum emission wavelength, and significantly decreased the CIE y value at the same doping proportion.

It can be seen that through the introduction of the ortho-substituent into the fluorene ring, that is, the introduction of R″ in Formula 4, the compounds of the present disclosure can also significantly improve the device performance when the doping proportion is changed.

TABLE 3 Part device structures in Device Examples 6 and 7 Device ID HIL HTL EBL EML HBL ETL Example Compound Compound Compound Compound Compound Compound 6 HI HT EB BH: HB (50 Å) ET:Liq (100 Å) (1200 Å) (50 Å) compound (40:60) 419 (98:2) (120 Å) (250 Å) Example Compound Compound Compound Compound Compound Compound 7 HI HT EB BH: HB (50 Å) ET:Liq (100 Å) (1200 Å) (50 Å) compound (40:60) 422 (98:2) (120 Å) (250 Å)

Structures of the new materials used in the devices are shown as follows:

Discussion:

Example 6 (with a doping proportion of 2%) exhibits EQE of 9.72%, maximum emission wavelength of 461 nm, CIE of (0.134, 0.123), LT97 of 879 h, and a half-peak width of 33.7 nm. Compared with Comparative Example 1, Example 6 has improved the lifetime by 224% and the EQE by 20.5%, narrowed the half-peak width by 3.4 nm, and achieved a blue-shift of 8 nm at the same doping proportion. Based on the excellent device performance of Example 2, Example 6 has further improved the lifetime by 58.9% and the EQE by 1.6%, and narrowed the half-peak width by 0.6 nm. Example 7 (with a doping proportion of 2%) exhibits EQE of 9.59%, maximum emission wavelength of 460 nm, CIE of (0.134, 0.114), LT97 of 395 h, and a half-peak width of 30.2 nm. Compared with Comparative Example 1, Example 7 has improved the lifetime by 45.7% and the EQE by 18.9%, narrowed the half-peak width by 6.9 nm, and achieved a blue-shift of 9 nm at the same doping proportion. Moreover, based on Example 6, Example 7 has further narrowed the half-peak width by 3.5 nm.

It can be seen that through the introduction of the ortho-substituent into the fluorene ring, that is, the introduction of R″ in Formula 4, the compounds of the present disclosure can more significantly improve the EQE and the lifetime of the devices by introducing deuterated alkyl compared with common alkyl. Meanwhile, the half-peak width can be further narrowed.

TABLE 4 Part device structures in Device Examples 8 and 9 Device ID HIL HTL EBL EML HBL ETL Example Compound Compound Compound Compound Compound Compound 8 HI HT EB BH: HB (50 Å) ET:Liq (100 Å) (1200 Å) (50 Å) compound (40:60) 2333 (98:2) (120 Å) (250 Å) Example Compound Compound Compound Compound Compound Compound 9 HI HT EB BH: HB (50 Å) ET:Liq (100 Å) (1200 Å) (50 Å) compound (40:60) 2334 (98:2) (120 Å) (250 Å)

Structures of the new materials used in the devices are shown as follows:

Discussion:

Example 8 (with a doping proportion of 2%) exhibits EQE of 9.54%, maximum emission wavelength of 460 nm, CIE of (0.135, 0.114), LT97 of 796 h, and a half-peak width of 33.6 nm. Compared with Comparative Example 1, Example 8 has improved the lifetime by 193% and the EQE by 18.3%, narrowed the half-peak width by 3.5 nm, and achieved a blue-shift of 9 nm at the same doping proportion. Based on the excellent device performance of Example 2, Example 8 has further improved the lifetime by 43.9% and narrowed the half-peak width by 0.7 nm.

Example 9 (with a doping proportion of 2%) exhibits EQE of 9.16%, maximum emission wavelength of 456 nm, CIE of (0.139, 0.090), LT97 of 683 h, and a half-peak width of 32.2 nm. Compared with Comparative Example 1, Example 9 has improved the lifetime by 152% and the EQE by 13.6%, narrowed the half-peak width by 4.9 nm, and achieved a blue-shift of 13 nm at the same doping proportion. Based on the excellent device performance of Example 1, Example 9 has further improved the lifetime by 89.7% and narrowed the half-peak width by 0.5 nm.

It can be seen that through the introduction of an electron-deficient group into the aromatic ring directly connecting to nitrogen,which is in the substituent R of Formula 3, the maximum emission wavelength can be further blue-shifted and the device lifetime can be further improved, while maintaining a longer device lifetime and higher EQE.

TABLE 5 Part device structures in Device Examples 10 and 11 Device ID HIL HTL EBL EML HBL ETL Example Compound Compound Compound Compound Compound Compound 10 HI HT EB BH: HB (50 Å) ET:Liq (100 Å) (1200 Å) (50 Å) compound (40:60) 506 (98:2) (120 Å) (250 Å) Example Compound Compound Compound Compound Compound Compound 11 HI HT EB BH: HB (50 Å) ET:Liq (100 Å) (1200 Å) (50 Å) compound (40:60) 2350 (98:2) (120 Å) (250 Å)

Structures of the new materials used in the devices are shown as follows:

Example 10 (with a doping proportion of 2%) exhibits EQE of 9.57%, maximum emission wavelength of 461 nm, CIE of (0.135, 0.117), LT97 of 382 h, and a half-peak width of 33.5 nm. Compared with Comparative Example 1, Example 10 has improved the lifetime by 40.9% and the EQE by 18.7%, narrowed the half-peak width by 3.6 nm, and achieved a blue-shift of 8 nm at the same doping proportion.

It can be seen that through further substitution in the fluorene ring in Formula 4, that is, an aryl substituent further included in R′ in Formula 4, the EQE and the lifetime of the device can also be improved, thereby improving the overall performance of the device.

Example 11 (with a doping proportion of 2%) exhibits EQE of 9.35%, maximum emission wavelength of 463 nm, CIE of (0.136, 0.137), LT97 of 459 h, and a half-peak width of 31.5 nm. Compared with Comparative Example 1, Example 11 has improved the lifetime by about 69.4% and the EQE by 16%, narrowed the half-peak width by 5.6 nm, and achieved a blue-shift of 6 nm at the same doping proportion. Moreover, compared with Example 2 in which the half-peak width has been narrowed by 2.8 nm, Example 11 has further narrowed the half-peak width by 2.8 nm.

It is seen from the above comparison that when the substituents of the nitrogen atom, that is, Ar₂ and R in Formula 3 remain the same, the introduction of substituents into R₃ and R₈ in Formula 5 can achieve a narrower half-peak width while maintaining relatively high EQE and lifetime, thereby further improving performance

In summary, for compounds with different structures of A such as pyrene and chrysene in the present disclosure, the introduction of the ortho-substituent into the fluorene ring, that is, the introduction of R″ in Formula 4 exhibits significant improvements in overall blue light-emitting performance. In addition, the further introduction of substituents at different positions, such as the introduction of substituents into R₃ and R₈ in Formula 5 and the introduction of an electron-deficient group into the aromatic ring joined to the nitrogen atom in Formula 3, can achieve longer device lifetime, higher EQE, narrower half-peak width, and deep-blue emission with CIE y being less than 0.14, thereby achieving a very large improvement in device performance. These compounds are of great help to the commercial use of blue light-emitting materials in OLEDs.

It should be understood that various embodiments described herein are merely examples and not intended to limit the scope of the present disclosure. Therefore, it is apparent to those skilled in the art that the present disclosure as claimed may include variations from specific embodiments and preferred embodiments described herein. Many of materials and structures described herein may be substituted with other materials and structures without departing from the spirit of the present disclosure. It should be understood that various theories as to why the present disclosure works are not intended to be limitative. 

What is claimed is:
 1. A compound having Formula 1:

in Formula 1, A is substituted or unsubstituted aryl having 10 to 60 ring carbon atoms or substituted or unsubstituted heteroaryl having 10 to 60 ring atoms; n is an integer greater than or equal to 1, m is an integer greater than or equal to 0, and n+m is greater than or equal to 2; when n is greater than or equal to 2, B may be the same or different structures; when m is greater than or equal to 2, E may be the same or different structures; E has a structure represented by Formula 2:

in Formula 2, * represents a position where E is joined to A; Ar and Ar₁ are each independently selected from the group consisting of: substituted or unsubstituted aryl having 6 to 30 ring carbon atoms and substituted or unsubstituted heteroaryl having 3 to 30 ring atoms; B has a structure represented by Formula 3:

in Formula 3, * represents a position where B is joined to A; wherein R is selected from the group consisting of: substituted or unsubstituted aryl having 6 to 30 ring carbon atoms and substituted or unsubstituted heteroaryl having 3 to 30 ring atoms; and when R is selected from the aryl, R is not substituted or unsubstituted naphthyl; wherein Ar₂ has a structure represented by Formula 4:

and Ar₂ comprises only one fluorene ring structure, azafluorene ring structure, spirobifluorene ring structure, or azaspirobifluorene ring structure; in Formula 4, * represents a position where Ar₂ is joined to N shown in Formula 3; X is C or Si; L is selected from a single bond, substituted or unsubstituted arylene having 6 to 60 carbon atoms, or substituted or unsubstituted heteroarylene having 3 to 60 carbon atoms; X₁ to X₈ are each independently selected from C, CR′, or N, and two adjacent C are present in X₁ to X₄, wherein one of the two adjacent C is joined to L, and the other one of the two adjacent C is joined to R″; wherein R_(a), R_(b), and R′ are each independently selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a thiol group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof; wherein R″ is independently selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a thiol group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof; and wherein in Formula 4, substituents R_(a) and R_(b) can be optionally joined to form a ring, and two adjacent substituents R′ can be optionally joined to form a ring.
 2. The compound of claim 1, wherein A in Formula 1 is selected from a structure represented by any one of Formula Ito Formula IX:

in Formula Ito Formula IX, n of R₁ to R_(i) have the structure of B represented by Formula 3, and m of R₁ to R_(i) have the structure of E represented by Formula 2; n is 1, 2, 3, or 4, m is 0, 1, 2, 3, or 4, and n+m is greater than or equal to 2; R_(i) represents the R with the largest number in any one of Formula Ito Formula IX; the rest of R₁ to R_(i) are each independently selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, and combinations thereof; X_(a) and X_(b) are each independently selected from the group consisting of: CR_(x)R_(y), SiR_(x)R_(y), NR_(x), O, S, and Se; R_(x) and R_(y) are each independently selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a thiol group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof; and substituents R_(x) and R_(y) can be optionally joined to form a ring.
 3. The compound of claim 2, wherein in Formula Ito Formula IX, two of R₁ to R₁ have the structure of B represented by Formula 3, and none of R₁ to R₁ have the structure of E represented by Formula 2, wherein R₁ represents the R with the largest number in any one of Formula I to Formula IX.
 4. The compound of claim 2, having a structure represented by one of Formula 5 to Formula 13:

in Formula 5 to Formula 13, R₁ to R₁₂ are each independently selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, and combinations thereof; X_(a) and X_(b) are each independently selected from the group consisting of: CR_(x)R_(y), SiR_(x)R_(y), NR_(x), O, S, and Se; R_(x) and R_(y) are each independently selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a thiol group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof; substituents R_(x) and R_(y) can be optionally joined to form a ring; and R, R_(a), R_(b), R″, L, X, and X₁ to X₈ have same ranges as defined in claim
 1. 5. The compound of claim 4, wherein in Formula 5 to Formula 13, each L is joined to X₂, or each L is joined to X₃.
 6. The compound of claim 4, wherein L is independently selected from a single bond, substituted or unsubstituted arylene having 6 to 12 carbon atoms, or substituted or unsubstituted heteroarylene having 3 to 12 carbon atoms; preferably, L is independently selected from a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene , or substituted or unsubstituted naphthylene.
 7. The compound of claim 4, wherein X₁ to X₈ are each independently selected from C or CR′, wherein R′ is each independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 10 ring carbon atoms, substituted or unsubstituted aryl having 6 to 12 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 12 carbon atoms, a nitrile group, or combinations thereof; preferably, R′ is each independently selected from hydrogen, deuterium, fluorine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, cyclohexyl, phenyl, or nitrile.
 8. The compound of claim 4, wherein R″ is selected from halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, or substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms; preferably, R″ is selected from the group consisting of: fluorine, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, t-butyl, cyclopentyl, neopentyl, cyclohexyl, 4,4-dimethylcyclohexyl, deuterated methyl, deuterated ethyl, deuterated n-propyl, deuterated isopropyl, deuterated cyclopropyl, deuterated n-butyl, deuterated isobutyl, deuterated t-butyl, deuterated cyclopentyl, deuterated neopentyl, deuterated cyclohexyl, and deuterated 4,4-dimethylcyclohexyl.
 9. The compound of claim 4, wherein R_(a) and R_(b) are each independently selected from substituted or unsubstituted alkyl having 1 to 6 carbon atoms or substituted or unsubstituted cycloalkyl having 3 to 10 ring carbon atoms, and R_(a) and R_(b) are not joined to form a ring; preferably, R_(a) and R_(b) are each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or t-butyl, and R_(a) and R_(b) are not joined to form a ring.
 10. The compound of claim 4, wherein R in Formula 3 has a structure represented by Formula 17:

in Formula 17, * represents a position where R is joined to N shown in Formula 3; wherein the ring Ar₃ is aryl having 6 to 30 ring carbon atoms or heteroaryl having 3 to 30 ring atoms; and when the ring Ar₃ is aryl, the ring Ar₃ is not a naphthalene ring structure; wherein R_(e) represents mono-substitution, multi-substitution, or non-substitution; and R_(e) is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a thiol group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof; preferably, R_(e) is selected from the group consisting of: halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a thiol group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof; more preferably, R_(e) is selected from the group consisting of: fluorine, nitrile, isonitrile, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, and substituted or unsubstituted aryl having 6 to 12 carbon atoms.
 11. The compound of claim 4, wherein R in Formula 3 has a structure represented by Formula 14:

in Formula 14, * represents a position where R is joined to N shown in Formula 3; wherein the ring Ar₃ is aryl having 6 to 30 ring carbon atoms or heteroaryl having 3 to 30 ring atoms; and when the ring Ar₃ is aryl, the ring Ar₃ is not a naphthalene ring structure; R_(c) represents ortho-substitution of the position where R is joined to N shown in Formula 3, and R_(d) represents mono-substitution, multi-substitution, or non-substitution; wherein R_(d) is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a thiol group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof; wherein R_(e) is selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a thiol group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof.
 12. The compound of claim 10, wherein the ring Ar₃ is selected from any one of the following ring structures: a benzene ring, a triphenylene ring, a tetraphenylene ring, a phenanthrene ring, an anthracene ring, an indene ring, a fluorene ring, a chrysene ring, an indole ring, a carbazole ring, a benzofuran ring, a dibenzofuran ring, a benzosilole ring, a dibenzosilole ring, a benzothiophene ring, a dibenzothiophene ring, a dibenzoselenophene ring, or aza-structures of any one of the above ring structures.
 13. The compound of claim 11, wherein the ring Ar₃ is selected from any one of the following ring structures: a benzene ring, a triphenylene ring, a tetraphenylene ring, a phenanthrene ring, an anthracene ring, an indene ring, a fluorene ring, a chrysene ring, an indole ring, a carbazole ring, a benzofuran ring, a dibenzofuran ring, a benzosilole ring, a dibenzosilole ring, a benzothiophene ring, a dibenzothiophene ring, a dibenzoselenophene ring, or aza-structures of any one of the above ring structures.
 14. The compound of claim 11, wherein R_(c) is selected from methyl, deuterated methyl, ethyl, deuterated ethyl, n-propyl, deuterated n-propyl, isopropyl, deuterated isopropyl, cyclopropyl, deuterated cyclopropyl, n-butyl, deuterated n-butyl, isobutyl, deuterated isobutyl, t-butyl, deuterated t-butyl, cyclopentyl, deuterated cyclopentyl, neopentyl, deuterated neopentyl, cyclohexyl, deuterated cyclohexyl, 4,4-dimethylcyclohexyl, or deuterated 4,4-dimethylcyclohexyl, R_(d) represents non-substitution, or R_(d) represents mono-substitution and R_(d) is each independently selected from the group consisting of: substituted or unsubstituted aryl having 6 to 12 carbon atoms or substituted or unsubstituted heteroaryl having 3 to 12 carbon atoms; preferably, R_(d) is each independently selected from phenyl, biphenyl, or terphenyl.
 15. The compound of claim 1, wherein B is selected from the group consisting of the following structures:

in the above specific structures of B,

represents a position where B is joined to A.
 16. The compound of claim 15, wherein compounds 1 to 2398 have a structure represented by Formula 15: A-(—B)_(n)   Formula 15 wherein n in the structure of Formula 15 equals 2, and two B are the same; A and B in structures of compounds 1 to 2398 have structures listed in the following table, separately: A B Compound Structure Structure 1 A₁ B-1-1 2 A₁ B-1-2 3 A₁ B-1-3 4 A₁ B-1-4 5 A₁ B-1-5 6 A₁ B-1-6 7 A₁ B-1-7 8 A₁ B-1-8 9 A₁ B-1-9 10 A₁ B-1-10 11 A₁ B-1-11 12 A₁ B-1-12 13 A₁ B-1-13 14 A₁ B-1-14 15 A₁ B-1-15 16 A₁ B-1-16 17 A₁ B-1-17 18 A₁ B-1-18 19 A₁ B-1-19 20 A₁ B-1-20 21 A₁ B-1-21 22 A₁ B-1-22 23 A₁ B-1-23 24 A₁ B-1-24 25 A₁ B-1-25 26 A₁ B-1-26 27 A₁ B-1-27 28 A₁ B-1-28 29 A₁ B-1-29 30 A₁ B-1-30 31 A₁ B-1-31 32 A₁ B-1-32 33 A₁ B-1-33 34 A₁ B-1-34 35 A₁ B-1-35 36 A₁ B-1-36 37 A₁ B-1-37 38 A₁ B-1-38 39 A₁ B-1-39 40 A₁ B-1-40 41 A₁ B-1-41 42 A₁ B-1-42 43 A₁ B-1-43 44 A₁ B-1-44 45 A₁ B-1-45 46 A₁ B-1-46 47 A₁ B-1-47 48 A₁ B-1-48 49 A₁ B-1-49 50 A₁ B-1-50 51 A₁ B-1-51 52 A₁ B-1-52 53 A₁ B-1-53 54 A₁ B-1-54 55 A₁ B-1-55 56 A₁ B-1-56 57 A₁ B-1-57 58 A₁ B-1-58 59 A₁ B-1-59 60 A₁ B-1-60 61 A₁ B-1-61 62 A₁ B-1-62 63 A₁ B-1-63 64 A₁ B-1-64 65 A₁ B-1-65 66 A₁ B-1-66 67 A₁ B-1-67 68 A₁ B-1-68 69 A₁ B-1-69 70 A₁ B-1-70 71 A₁ B-1-71 72 A₁ B-1-72 73 A₁ B-2-1 74 A₁ B-2-2 75 A₁ B-2-3 76 A₁ B-2-4 77 A₁ B-2-5 78 A₁ B-2-6 79 A₁ B-2-7 80 A₁ B-2-8 81 A₁ B-2-9 82 A₁ B-2-10 83 A₁ B-2-11 84 A₁ B-2-12 85 A₁ B-2-13 86 A₁ B-2-14 87 A₁ B-2-15 88 A₁ B-2-16 89 A₁ B-2-17 90 A₁ B-2-18 91 A₁ B-2-19 92 A₁ B-2-20 93 A₁ B-2-21 94 A₁ B-2-22 95 A₁ B-2-23 96 A₁ B-2-24 97 A₁ B-2-25 98 A₁ B-2-26 99 A₁ B-2-27 100 A₁ B-2-28 101 A₁ B-2-29 102 A₁ B-2-30 103 A₁ B-2-31 104 A₁ B-2-32 105 A₁ B-2-33 106 A₁ B-2-34 107 A₁ B-2-35 108 A₁ B-2-36 109 A₁ B-2-37 110 A₁ B-2-38 111 A₁ B-2-39 112 A₁ B-2-40 113 A₁ B-2-41 114 A₁ B-2-42 115 A₁ B-2-43 116 A₁ B-2-44 117 A₁ B-2-45 118 A₁ B-2-46 119 A₁ B-2-47 120 A₁ B-2-48 121 A₁ B-2-49 122 A₁ B-2-50 123 A₁ B-2-51 124 A₁ B-2-52 125 A₁ B-2-53 126 A₁ B-2-54 127 A₁ B-2-55 128 A₁ B-2-56 129 A₁ B-2-57 130 A₁ B-2-58 131 A₁ B-2-59 132 A₁ B-2-60 133 A₁ B-2-61 134 A₁ B-2-62 135 A₁ B-2-63 136 A₁ B-2-64 137 A₁ B-2-65 138 A₁ B-2-66 139 A₁ B-2-67 140 A₁ B-2-68 141 A₁ B-2-69 142 A₁ B-2-70 143 A₁ B-2-71 144 A₁ B-2-72 145 A₁ B-2-73 146 A₁ B-2-74 147 A₁ B-2-75 148 A₁ B-2-76 149 A₁ B-2-77 150 A₁ B-2-78 151 A₁ B-2-79 152 A₁ B-2-80 153 A₁ B-2-81 154 A₁ B-2-82 155 A₁ B-2-83 156 A₁ B-2-84 157 A₁ B-2-85 158 A₁ B-2-86 159 A₁ B-2-87 160 A₁ B-2-88 161 A₁ B-2-89 162 A₁ B-2-90 163 A₁ B-2-91 164 A₁ B-2-92 165 A₁ B-2-93 166 A₁ B-2-94 167 A₁ B-2-95 168 A₁ B-2-96 169 A₁ B-2-97 170 A₁ B-2-98 171 A₁ B-2-99 172 A₁ B-2-100 173 A₁ B-2-101 174 A₁ B-2-102 175 A₁ B-2-103 176 A₁ B-2-104 177 A₁ B-2-105 178 A₁ B-2-106 179 A₁ B-2-107 180 A₁ B-2-108 181 A₁ B-2-109 182 A₁ B-2-110 183 A₁ B-2-111 184 A₁ B-2-112 185 A₁ B-2-113 186 A₁ B-2-114 187 A₁ B-2-115 188 A₁ B-2-116 189 A₁ B-2-117 190 A₁ B-2-118 191 A₁ B-2-119 192 A₁ B-2-120 193 A₁ B-2-121 194 A₁ B-2-122 195 A₁ B-2-123 196 A₁ B-2-124 197 A₁ B-2-125 198 A₁ B-2-126 199 A₁ B-2-127 200 A₁ B-2-128 201 A₁ B-2-129 202 A₁ B-2-130 203 A₁ B-2-131 204 A₁ B-2-132 205 A₁ B-2-133 206 A₁ B-2-134 207 A₁ B-2-135 208 A₁ B-2-136 209 A₁ B-2-137 210 A₁ B-2-138 211 A₁ B-2-139 212 A₁ B-2-140 213 A₁ B-2-141 214 A₁ B-2-142 215 A₁ B-2-143 216 A₁ B-2-144 217 A₁ B-2-145 218 A₁ B-2-146 219 A₁ B-2-147 220 A₁ B-2-148 221 A₁ B-2-149 222 A₁ B-2-150 223 A₁ B-2-151 224 A₁ B-2-152 225 A₁ B-2-153 226 A₁ B-2-154 227 A₁ B-2-155 228 A₁ B-2-156 229 A₁ B-2-157 230 A₁ B-2-158 231 A₁ B-2-159 232 A₁ B-2-160 233 A₁ B-2-161 234 A₁ B-2-162 235 A₁ B-2-163 236 A₁ B-2-164 237 A₁ B-2-165 238 A₁ B-2-166 239 A₁ B-2-167 240 A₁ B-2-168 241 A₁ B-2-169 242 A₁ B-2-170 243 A₁ B-2-171 244 A₁ B-2-172 245 A₁ B-2-173 246 A₁ B-2-174 247 A₁ B-2-175 248 A₁ B-2-176 249 A₁ B-2-177 250 A₁ B-2-178 251 A₁ B-2-179 252 A₁ B-2-180 253 A₁ B-2-181 254 A₁ B-2-182 255 A₁ B-2-183 256 A₁ B-2-184 257 A₁ B-2-185 258 A₁ B-2-186 259 A₁ B-2-187 260 A₁ B-2-188 261 A₁ B-2-189 262 A₁ B-2-190 263 A₁ B-2-191 264 A₁ B-2-192 265 A₁ B-2-193 266 A₁ B-2-194 267 A₁ B-2-195 268 A₁ B-2-196 269 A₁ B-2-197 270 A₁ B-2-198 271 A₁ B-2-199 272 A₁ B-2-200 273 A₁ B-2-201 274 A₁ B-2-202 275 A₁ B-2-203 276 A₁ B-2-204 277 A₁ B-2-205 278 A₁ B-2-206 279 A₁ B-2-207 280 A₁ B-2-208 281 A₁ B-2-209 282 A₁ B-2-210 283 A₁ B-2-211 284 A₁ B-2-212 285 A₁ B-2-213 286 A₁ B-2-214 287 A₁ B-2-215 288 A₁ B-2-216 289 A₁ B-2-217 290 A₁ B-2-218 291 A₁ B-3-1 292 A₁ B-3-2 293 A₁ B-3-3 294 A₁ B-3-4 295 A₁ B-3-5 296 A₁ B-3-6 297 A₁ B-3-7 298 A₁ B-3-8 299 A₁ B-3-9 300 A₁ B-3-10 301 A₁ B-3-11 302 A₁ B-3-12 303 A₁ B-3-13 304 A₁ B-3-14 305 A₁ B-3-15 306 A₁ B-3-16 307 A₁ B-3-17 308 A₁ B-3-18 309 A₁ B-3-19 310 A₁ B-3-20 311 A₁ B-3-21 312 A₁ B-3-22 313 A₁ B-3-23 314 A₁ B-3-24 315 A₁ B-3-25 316 A₁ B-3-26 317 A₁ B-3-27 318 A₁ B-3-28 319 A₁ B-3-29 320 A₁ B-3-30 321 A₁ B-3-31 322 A₁ B-3-32 323 A₁ B-3-33 324 A₁ B-3-34 325 A₁ B-3-35 326 A₁ B-3-36 327 A₁ B-3-37 328 A₁ B-3-38 329 A₁ B-3-39 330 A₁ B-3-40 331 A₁ B-3-41 332 A₁ B-3-42 333 A₁ B-3-43 334 A₁ B-3-44 335 A₁ B-3-45 336 A₁ B-3-46 337 A₁ B-3-47 338 A₁ B-3-48 339 A₁ B-3-49 340 A₁ B-3-50 341 A₁ B-3-51 342 A₁ B-3-52 343 A₁ B-3-53 344 A₁ B-3-54 345 A₁ B-3-55 346 A₁ B-3-56 347 A₁ B-3-57 348 A₁ B-3-58 349 A₁ B-3-59 350 A₁ B-3-60 351 A₁ B-3-61 352 A₁ B-3-62 353 A₁ B-3-63 354 A₁ B-3-64 355 A₁ B-3-65 356 A₁ B-3-66 357 A₁ B-3-67 358 A₁ B-3-68 359 A₁ B-3-69 360 A₁ B-3-70 361 A₁ B-3-71 362 A₁ B-3-72 363 A₁ B-3-73 364 A₁ B-3-74 365 A₁ B-3-75 366 A₁ B-3-76 367 A₁ B-3-77 368 A₁ B-3-78 369 A₁ B-3-79 370 A₁ B-3-80 371 A₁ B-3-81 372 A₁ B-3-82 373 A₁ B-3-83 374 A₁ B-3-84 375 A₁ B-3-85 376 A₁ B-3-86 377 A₁ B-3-87 378 A₁ B-3-88 379 A₁ B-3-89 380 A₁ B-3-90 381 A₁ B-3-91 382 A₁ B-3-92 383 A₁ B-3-93 384 A₁ B-3-94 385 A₁ B-3-95 386 A₁ B-3-96 387 A₁ B-3-97 388 A₁ B-3-98 389 A₁ B-3-99 390 A₁ B-3-100 391 A₁ B-3-101 392 A₁ B-3-102 393 A₁ B-3-103 394 A₁ B-3-104 395 A₁ B-3-105 396 A₁ B-3-106 397 A₁ B-3-107 398 A₁ B-3-108 399 A₁ B-3-109 400 A₁ B-3-110 401 A₁ B-3-111 402 A₁ B-3-112 403 A₁ B-3-113 404 A₁ B-3-114 405 A₁ B-3-115 406 A₁ B-3-116 407 A₁ B-3-117 408 A₁ B-3-118 409 A₁ B-3-119 410 A₁ B-3-120 411 A₁ B-3-121 412 A₁ B-3-122 413 A₁ B-3-123 414 A₁ B-3-124 415 A₁ B-3-125 416 A₁ B-3-126 417 A₁ B-3-127 418 A₁ B-3-128 419 A₁ B-3-129 420 A₁ B-3-130 421 A₁ B-3-131 422 A₁ B-3-132 423 A₁ B-3-133 424 A₁ B-3-134 425 A₁ B-3-135 426 A₁ B-3-136 427 A₁ B-3-137 428 A₁ B-3-138 429 A₁ B-3-139 430 A₁ B-3-140 431 A₁ B-3-141 432 A₁ B-3-142 433 A₁ B-3-143 434 A₁ B-3-144 435 A₁ B-3-145 436 A₁ B-3-146 437 A₁ B-3-147 438 A₁ B-3-148 439 A₁ B-3-149 440 A₁ B-3-150 441 A₁ B-3-151 442 A₁ B-3-152 443 A₁ B-3-153 444 A₁ B-3-154 445 A₁ B-3-155 446 A₁ B-3-156 447 A₁ B-3-157 448 A₁ B-3-158 449 A₁ B-3-159 450 A₁ B-3-160 451 A₁ B-3-161 452 A₁ B-3-162 453 A₁ B-3-163 454 A₁ B-3-164 455 A₁ B-3-165 456 A₁ B-3-166 457 A₁ B-3-167 458 A₁ B-3-168 459 A₁ B-3-169 460 A₁ B-3-170 461 A₁ B-3-171 462 A₁ B-3-172 463 A₁ B-3-173 464 A₁ B-3-174 465 A₁ B-3-175 466 A₁ B-3-176 467 A₁ B-3-177 468 A₁ B-3-178 469 A₁ B-3-179 470 A₁ B-3-180 471 A₁ B-3-181 472 A₁ B-3-182 473 A₁ B-3-183 474 A₁ B-3-184 475 A₁ B-3-185 476 A₁ B-3-186 477 A₁ B-3-187 478 A₁ B-3-188 479 A₁ B-3-189 480 A₁ B-3-190 481 A₁ B-3-191 482 A₁ B-3-192 483 A₁ B-3-193 484 A₁ B-3-194 485 A₁ B-3-195 486 A₁ B-3-196 487 A₁ B-3-197 488 A₁ B-3-198 489 A₁ B-3-199 490 A₁ B-3-200 491 A₁ B-3-201 492 A₁ B-3-202 493 A₁ B-3-203 494 A₁ B-3-204 495 A₁ B-3-205 496 A₁ B-3-206 497 A₁ B-3-207 498 A₁ B-3-208 499 A₁ B-3-209 500 A₁ B-3-210 501 A₁ B-3-211 502 A₁ B-3-212 503 A₁ B-3-213 504 A₁ B-3-214 505 A₁ B-3-215 506 A₁ B-3-216 507 A₁ B-3-217 508 A₁ B-3-218 509 A₁ B-4-1 510 A₁ B-4-2 511 A₁ B-4-3 512 A₁ B-4-4 513 A₁ B-4-5 514 A₁ B-4-6 515 A₁ B-4-7 516 A₁ B-4-8 517 A₁ B-4-9 518 A₁ B-4-10 519 A₁ B-4-11 520 A₁ B-4-12 521 A₁ B-4-13 522 A₁ B-4-14 523 A₁ B-4-15 524 A₁ B-4-16 525 A₁ B-4-17 526 A₁ B-4-18 527 A₁ B-4-19 528 A₁ B-4-20 529 A₁ B-4-21 530 A₁ B-4-22 531 A₁ B-4-23 532 A₁ B-4-24 533 A₁ B-4-25 534 A₁ B-4-26 535 A₁ B-4-27 536 A₁ B-4-28 537 A₁ B-4-29 538 A₁ B-4-30 539 A₁ B-4-31 540 A₁ B-4-32 541 A₁ B-4-33 542 A₁ B-4-34 543 A₁ B-4-35 544 A₁ B-4-36 545 A₁ B-4-37 546 A₁ B-4-38 547 A₁ B-4-39 548 A₁ B-4-40 549 A₁ B-4-41 550 A₁ B-4-42 551 A₁ B-4-43 552 A₁ B-4-44 553 A₁ B-4-45 554 A₁ B-4-46 555 A₁ B-4-47 556 A₁ B-4-48 557 A₁ B-4-49 558 A₁ B-4-50 559 A₁ B-4-51 560 A₁ B-4-52 561 A₁ B-4-53 562 A₁ B-4-54 563 A₁ B-4-55 564 A₁ B-4-56 565 A₁ B-4-57 566 A₁ B-4-58 567 A₁ B-4-59 568 A₁ B-4-60 569 A₁ B-4-61 570 A₁ B-4-62 571 A₁ B-4-63 572 A₁ B-4-64 573 A₁ B-4-65 574 A₁ B-4-66 575 A₁ B-4-67 576 A₁ B-4-68 577 A₁ B-4-69 578 A₁ B-4-70 579 A₁ B-4-71 580 A₁ B-4-72 581 A₁ B-5-1 582 A₁ B-5-2 583 A₁ B-5-3 584 A₁ B-5-4 585 A₁ B-5-5 586 A₁ B-5-6 587 A₁ B-5-7 588 A₁ B-5-8 589 A₁ B-5-9 590 A₁ B-5-10 591 A₁ B-5-11 592 A₁ B-5-12 593 A₁ B-5-13 594 A₁ B-5-14 595 A₁ B-5-15 596 A₁ B-5-16 597 A₁ B-5-17 598 A₁ B-5-18 599 A₁ B-5-19 600 A₁ B-5-20 601 A₁ B-5-21 602 A₁ B-5-22 603 A₁ B-5-23 604 A₁ B-5-24 605 A₁ B-5-25 606 A₁ B-5-26 607 A₁ B-5-27 608 A₁ B-5-28 609 A₁ B-5-29 610 A₁ B-5-30 611 A₁ B-5-31 612 A₁ B-5-32 613 A₁ B-5-33 614 A₁ B-5-34 615 A₁ B-5-35 616 A₁ B-5-36 617 A₁ B-5-37 618 A₁ B-5-38 619 A₁ B-5-39 620 A₁ B-5-40 621 A₁ B-5-41 622 A₁ B-5-42 623 A₁ B-5-43 624 A₁ B-5-44 625 A₁ B-5-45 626 A₁ B-5-46 627 A₁ B-5-47 628 A₁ B-5-48 629 A₁ B-5-49 630 A₁ B-5-50 631 A₁ B-5-51 632 A₁ B-5-52 633 A₁ B-5-53 634 A₁ B-5-54 635 A₁ B-5-55 636 A₁ B-5-56 637 A₁ B-5-57 638 A₁ B-5-58 639 A₁ B-5-59 640 A₁ B-5-60 641 A₁ B-5-61 642 A₁ B-5-62 643 A₁ B-5-63 644 A₁ B-5-64 645 A₁ B-5-65 646 A₁ B-5-66 647 A₁ B-5-67 648 A₁ B-5-68 649 A₁ B-5-69 650 A₁ B-5-70 651 A₁ B-5-71 652 A₁ B-5-72 653 A₁ B-6-1 654 A₁ B-6-2 655 A₁ B-6-3 656 A₁ B-6-4 657 A₁ B-6-5 658 A₁ B-6-6 659 A₁ B-6-7 660 A₁ B-6-8 661 A₁ B-6-9 662 A₁ B-6-10 663 A₁ B-6-11 664 A₁ B-6-12 665 A₁ B-6-13 666 A₁ B-6-14 667 A₁ B-6-15 668 A₁ B-6-16 669 A₁ B-6-17 670 A₁ B-6-18 671 A₂ B-1-1 672 A₂ B-1-2 673 A₂ B-1-3 674 A₂ B-1-4 675 A₂ B-1-5 676 A₂ B-1-6 677 A₂ B-1-7 678 A₂ B-1-8 679 A₂ B-1-9 680 A₂ B-1-10 681 A₂ B-1-11 682 A₂ B-1-12 683 A₂ B-1-13 684 A₂ B-1-14 685 A₂ B-1-15 686 A₂ B-1-16 687 A₂ B-1-17 688 A₂ B-1-18 689 A₂ B-1-19 690 A₂ B-1-20 691 A₂ B-1-21 692 A₂ B-1-22 693 A₂ B-1-23 694 A₂ B-1-24 695 A₂ B-1-25 696 A₂ B-1-26 697 A₂ B-1-27 698 A₂ B-1-28 699 A₂ B-1-29 700 A₂ B-1-30 701 A₂ B-1-31 702 A₂ B-1-32 703 A₂ B-1-33 704 A₂ B-1-34 705 A₂ B-1-35 706 A₂ B-1-36 707 A₂ B-1-37 708 A₂ B-1-38 709 A₂ B-1-39 710 A₂ B-1-40 711 A₂ B-1-41 712 A₂ B-1-42 713 A₂ B-1-43 714 A₂ B-1-44 715 A₂ B-1-45 716 A₂ B-1-46 717 A₂ B-1-47 718 A₂ B-1-48 719 A₂ B-1-49 720 A₂ B-1-50 721 A₂ B-1-51 722 A₂ B-1-52 723 A₂ B-1-53 724 A₂ B-1-54 725 A₂ B-1-55 726 A₂ B-1-56 727 A₂ B-1-57 728 A₂ B-1-58 729 A₂ B-1-59 730 A₂ B-1-60 731 A₂ B-1-61 732 A₂ B-1-62 733 A₂ B-1-63 734 A₂ B-1-64 735 A₂ B-1-65 736 A₂ B-1-66 737 A₂ B-1-67 738 A₂ B-1-68 739 A₂ B-1-69 740 A₂ B-1-70 741 A₂ B-1-71 742 A₂ B-1-72 743 A₂ B-2-1 744 A₂ B-2-2 745 A₂ B-2-3 746 A₂ B-2-4 747 A₂ B-2-5 748 A₂ B-2-6 749 A₂ B-2-7 750 A₂ B-2-8 751 A₂ B-2-9 752 A₂ B-2-10 753 A₂ B-2-11 754 A₂ B-2-12 755 A₂ B-2-13 756 A₂ B-2-14 757 A₂ B-2-15 758 A₂ B-2-16 759 A₂ B-2-17 760 A₂ B-2-18 761 A₂ B-2-19 762 A₂ B-2-20 763 A₂ B-2-21 764 A₂ B-2-22 765 A₂ B-2-23 766 A₂ B-2-24 767 A₂ B-2-25 768 A₂ B-2-26 769 A₂ B-2-27 770 A₂ B-2-28 771 A₂ B-2-29 772 A₂ B-2-30 773 A₂ B-2-31 774 A₂ B-2-32 775 A₂ B-2-33 776 A₂ B-2-34 777 A₂ B-2-35 778 A₂ B-2-36 779 A₂ B-2-37 780 A₂ B-2-38 781 A₂ B-2-39 782 A₂ B-2-40 783 A₂ B-2-41 784 A₂ B-2-42 785 A₂ B-2-43 786 A₂ B-2-44 787 A₂ B-2-45 788 A₂ B-2-46 789 A₂ B-2-47 790 A₂ B-2-48 791 A₂ B-2-49 792 A₂ B-2-50 793 A₂ B-2-51 794 A₂ B-2-52 795 A₂ B-2-53 796 A₂ B-2-54 797 A₂ B-2-55 798 A₂ B-2-56 799 A₂ B-2-57 800 A₂ B-2-58 801 A₂ B-2-59 802 A₂ B-2-60 803 A₂ B-2-61 804 A₂ B-2-62 805 A₂ B-2-63 806 A₂ B-2-64 807 A₂ B-2-65 808 A₂ B-2-66 809 A₂ B-2-67 810 A₂ B-2-68 811 A₂ B-2-69 812 A₂ B-2-70 813 A₂ B-2-71 814 A₂ B-2-72 815 A₂ B-2-73 816 A₂ B-2-74 817 A₂ B-2-75 818 A₂ B-2-76 819 A₂ B-2-77 820 A₂ B-2-78 821 A₂ B-2-79 822 A₂ B-2-80 823 A₂ B-2-81 824 A₂ B-2-82 825 A₂ B-2-83 826 A₂ B-2-84 827 A₂ B-2-85 828 A₂ B-2-86 829 A₂ B-2-87 830 A₂ B-2-88 831 A₂ B-2-89 832 A₂ B-2-90 833 A₂ B-2-91 834 A₂ B-2-92 835 A₂ B-2-93 836 A₂ B-2-94 837 A₂ B-2-95 838 A₂ B-2-96 839 A₂ B-2-97 840 A₂ B-2-98 841 A₂ B-2-99 842 A₂ B-2-100 843 A₂ B-2-101 844 A₂ B-2-102 845 A₂ B-2-103 846 A₂ B-2-104 847 A₂ B-2-105 848 A₂ B-2-106 849 A₂ B-2-107 850 A₂ B-2-108 851 A₂ B-2-109 852 A₂ B-2-110 853 A₂ B-2-111 854 A₂ B-2-112 855 A₂ B-2-113 856 A₂ B-2-114 857 A₂ B-2-115 858 A₂ B-2-116 859 A₂ B-2-117 860 A₂ B-2-118 861 A₂ B-2-119 862 A₂ B-2-120 863 A₂ B-2-121 864 A₂ B-2-122 865 A₂ B-2-123 866 A₂ B-2-124 867 A₂ B-2-125 868 A₂ B-2-126 869 A₂ B-2-127 870 A₂ B-2-128 871 A₂ B-2-129 872 A₂ B-2-130 873 A₂ B-2-131 874 A₂ B-2-132 875 A₂ B-2-133 876 A₂ B-2-134 877 A₂ B-2-135 878 A₂ B-2-136 879 A₂ B-2-137 880 A₂ B-2-138 881 A₂ B-2-139 882 A₂ B-2-140 883 A₂ B-2-141 884 A₂ B-2-142 885 A₂ B-2-143 886 A₂ B-2-144 887 A₂ B-2-145 888 A₂ B-2-146 889 A₂ B-2-147 890 A₂ B-2-148 891 A₂ B-2-149 892 A₂ B-2-150 893 A₂ B-2-151 894 A₂ B-2-152 895 A₂ B-2-153 896 A₂ B-2-154 897 A₂ B-2-155 898 A₂ B-2-156 899 A₂ B-2-157 900 A₂ B-2-158 901 A₂ B-2-159 902 A₂ B-2-160 903 A₂ B-2-161 904 A₂ B-2-162 905 A₂ B-2-163 906 A₂ B-2-164 907 A₂ B-2-165 908 A₂ B-2-166 909 A₂ B-2-167 910 A₂ B-2-168 911 A₂ B-3-1 912 A₂ B-3-2 913 A₂ B-3-3 914 A₂ B-3-4 915 A₂ B-3-5 916 A₂ B-3-6 917 A₂ B-3-7 918 A₂ B-3-8 919 A₂ B-3-9 920 A₂ B-3-10 921 A₂ B-3-11 922 A₂ B-3-12 923 A₂ B-3-13 924 A₂ B-3-14 925 A₂ B-3-15 926 A₂ B-3-16 927 A₂ B-3-17 928 A₂ B-3-18 929 A₂ B-3-19 930 A₂ B-3-20 931 A₂ B-3-21 932 A₂ B-3-22 933 A₂ B-3-23 934 A₂ B-3-24 935 A₂ B-3-25 936 A₂ B-3-26 937 A₂ B-3-27 938 A₂ B-3-28 939 A₂ B-3-29 940 A₂ B-3-30 941 A₂ B-3-31 942 A₂ B-3-32 943 A₂ B-3-33 944 A₂ B-3-34 945 A₂ B-3-35 946 A₂ B-3-36 947 A₂ B-3-37 948 A₂ B-3-38 949 A₂ B-3-39 950 A₂ B-3-40 951 A₂ B-3-41 952 A₂ B-3-42 953 A₂ B-3-43 954 A₂ B-3-44 955 A₂ B-3-45 956 A₂ B-3-46 957 A₂ B-3-47 958 A₂ B-3-48 959 A₂ B-3-49 960 A₂ B-3-50 961 A₂ B-3-51 962 A₂ B-3-52 963 A₂ B-3-53 964 A₂ B-3-54 965 A₂ B-3-55 966 A₂ B-3-56 967 A₂ B-3-57 968 A₂ B-3-58 969 A₂ B-3-59 970 A₂ B-3-60 971 A₂ B-3-61 972 A₂ B-3-62 973 A₂ B-3-63 974 A₂ B-3-64 975 A₂ B-3-65 976 A₂ B-3-66 977 A₂ B-3-67 978 A₂ B-3-68 979 A₂ B-3-69 980 A₂ B-3-70 981 A₂ B-3-71 982 A₂ B-3-72 983 A₂ B-3-73 984 A₂ B-3-74 985 A₂ B-3-75 986 A₂ B-3-76 987 A₂ B-3-77 988 A₂ B-3-78 989 A₂ B-3-79 990 A₂ B-3-80 991 A₂ B-3-81 992 A₂ B-3-82 993 A₂ B-3-83 994 A₂ B-3-84 995 A₂ B-3-85 996 A₂ B-3-86 997 A₂ B-3-87 998 A₂ B-3-88 999 A₂ B-3-89 1000 A₂ B-3-90 1001 A₂ B-3-91 1002 A₂ B-3-92 1003 A₂ B-3-93 1004 A₂ B-3-94 1005 A₂ B-3-95 1006 A₂ B-3-96 1007 A₂ B-3-97 1008 A₂ B-3-98 1009 A₂ B-3-99 1010 A₂ B-3-100 1011 A₂ B-3-101 1012 A₂ B-3-102 1013 A₂ B-3-103 1014 A₂ B-3-104 1015 A₂ B-3-105 1016 A₂ B-3-106 1017 A₂ B-3-107 1018 A₂ B-3-108 1019 A₂ B-3-109 1020 A₂ B-3-110 1021 A₂ B-3-111 1022 A₂ B-3-112 1023 A₂ B-3-113 1024 A₂ B-3-114 1025 A₂ B-3-115 1026 A₂ B-3-116 1027 A₂ B-3-117 1028 A₂ B-3-118 1029 A₂ B-3-119 1030 A₂ B-3-120 1031 A₂ B-3-121 1032 A₂ B-3-122 1033 A₂ B-3-123 1034 A₂ B-3-124 1035 A₂ B-3-125 1036 A₂ B-3-126 1037 A₂ B-3-127 1038 A₂ B-3-128 1039 A₂ B-3-129 1040 A₂ B-3-130 1041 A₂ B-3-131 1042 A₂ B-3-132 1043 A₂ B-3-133 1044 A₂ B-3-134 1045 A₂ B-3-135 1046 A₂ B-3-136 1047 A₂ B-3-137 1048 A₂ B-3-138 1049 A₂ B-3-139 1050 A₂ B-3-140 1051 A₂ B-3-141 1052 A₂ B-3-142 1053 A₂ B-3-143 1054 A₂ B-3-144 1055 A₂ B-3-145 1056 A₂ B-3-146 1057 A₂ B-3-147 1058 A₂ B-3-148 1059 A₂ B-3-149 1060 A₂ B-3-150 1061 A₂ B-3-151 1062 A₂ B-3-152 1063 A₂ B-3-153 1064 A₂ B-3-154 1065 A₂ B-3-155 1066 A₂ B-3-156 1067 A₂ B-3-157 1068 A₂ B-3-158 1069 A₂ B-3-159 1070 A₂ B-3-160 1071 A₂ B-3-161 1072 A₂ B-3-162 1073 A₂ B-3-163 1074 A₂ B-3-164 1075 A₂ B-3-165 1076 A₂ B-3-166 1077 A₂ B-3-167 1078 A₂ B-3-168 1079 A₂ B-4-1 1080 A₂ B-4-2 1081 A₂ B-4-3 1082 A₂ B-4-4 1083 A₂ B-4-5 1084 A₂ B-4-6 1085 A₂ B-4-7 1086 A₂ B-4-8 1087 A₂ B-4-9 1088 A₂ B-4-10 1089 A₂ B-4-11 1090 A₂ B-4-12 1091 A₂ B-4-13 1092 A₂ B-4-14 1093 A₂ B-4-15 1094 A₂ B-4-16 1095 A₂ B-4-17 1096 A₂ B-4-18 1097 A₂ B-4-19 1098 A₂ B-4-20 1099 A₂ B-4-21 1100 A₂ B-4-22 1101 A₂ B-4-23 1102 A₂ B-4-24 1103 A₂ B-4-25 1104 A₂ B-4-26 1105 A₂ B-4-27 1106 A₂ B-4-28 1107 A₂ B-4-29 1108 A₂ B-4-30 1109 A₂ B-4-31 1110 A₂ B-4-32 1111 A₂ B-4-33 1112 A₂ B-4-34 1113 A₂ B-4-35 1114 A₂ B-4-36 1115 A₂ B-4-37 1116 A₂ B-4-38 1117 A₂ B-4-39 1118 A₂ B-4-40 1119 A₂ B-4-41 1120 A₂ B-4-42 1121 A₂ B-4-43 1122 A₂ B-4-44 1123 A₂ B-4-45 1124 A₂ B-4-46 1125 A₂ B-4-47 1126 A₂ B-4-48 1127 A₂ B-4-49 1128 A₂ B-4-50 1129 A₂ B-4-51 1130 A₂ B-4-52 1131 A₂ B-4-53 1132 A₂ B-4-54 1133 A₂ B-4-55 1134 A₂ B-4-56 1135 A₂ B-4-57 1136 A₂ B-4-58 1137 A₂ B-4-59 1138 A₂ B-4-60 1139 A₂ B-4-61 1140 A₂ B-4-62 1141 A₂ B-4-63 1142 A₂ B-4-64 1143 A₂ B-4-65 1144 A₂ B-4-66 1145 A₂ B-4-67 1146 A₂ B-4-68 1147 A₂ B-4-69 1148 A₂ B-4-70 1149 A₂ B-4-71 1150 A₂ B-4-72 1151 A₂ B-5-1 1152 A₂ B-5-2 1153 A₂ B-5-3 1154 A₂ B-5-4 1155 A₂ B-5-5 1156 A₂ B-5-6 1157 A₂ B-5-7 1158 A₂ B-5-8 1159 A₂ B-5-9 1160 A₂ B-5-10 1161 A₂ B-5-11 1162 A₂ B-5-12 1163 A₂ B-5-13 1164 A₂ B-5-14 1165 A₂ B-5-15 1166 A₂ B-5-16 1167 A₂ B-5-17 1168 A₂ B-5-18 1169 A₂ B-5-19 1170 A₂ B-5-20 1171 A₂ B-5-21 1172 A₂ B-5-22 1173 A₂ B-5-23 1174 A₂ B-5-24 1175 A₂ B-5-25 1176 A₂ B-5-26 1177 A₂ B-5-27 1178 A₂ B-5-28 1179 A₂ B-5-29 1180 A₂ B-5-30 1181 A₂ B-5-31 1182 A₂ B-5-32 1183 A₂ B-5-33 1184 A₂ B-5-34 1185 A₂ B-5-35 1186 A₂ B-5-36 1187 A₂ B-5-37 1188 A₂ B-5-38 1189 A₂ B-5-39 1190 A₂ B-5-40 1191 A₂ B-5-41 1192 A₂ B-5-42 1193 A₂ B-5-43 1194 A₂ B-5-44 1195 A₂ B-5-45 1196 A₂ B-5-46 1197 A₂ B-5-47 1198 A₂ B-5-48 1199 A₂ B-5-49 1200 A₂ B-5-50 1201 A₂ B-5-51 1202 A₂ B-5-52 1203 A₂ B-5-53 1204 A₂ B-5-54 1205 A₂ B-5-55 1206 A₂ B-5-56 1207 A₂ B-5-57 1208 A₂ B-5-58 1209 A₂ B-5-59 1210 A₂ B-5-60 1211 A₂ B-5-61 1212 A₂ B-5-62 1213 A₂ B-5-63 1214 A₂ B-5-64 1215 A₂ B-5-65 1216 A₂ B-5-66 1217 A₂ B-5-67 1218 A₂ B-5-68 1219 A₂ B-5-69 1220 A₂ B-5-70 1221 A₂ B-5-71 1222 A₂ B-5-72 1223 A₂ B-6-1 1224 A₂ B-6-2 1225 A₂ B-6-3 1226 A₂ B-6-4 1227 A₂ B-6-5 1228 A₂ B-6-6 1229 A₂ B-6-7 1230 A₂ B-6-8 1231 A₂ B-6-9 1232 A₂ B-6-10 1233 A₂ B-6-11 1234 A₂ B-6-12 1235 A₂ B-6-13 1236 A₂ B-6-14 1237 A₂ B-6-15 1238 A₂ B-6-16 1239 A₂ B-6-17 1240 A₂ B-6-18 1241 A₃ B-1-1 1242 A₃ B-1-5 1243 A₃ B-1-9 1244 A₃ B-1-13 1245 A₃ B-1-17 1246 A₃ B-1-21 1247 A₃ B-1-25 1248 A₃ B-1-29 1249 A₃ B-1-33 1250 A₃ B-1-37 1251 A₃ B-1-41 1252 A₃ B-1-45 1253 A₃ B-1-49 1254 A₃ B-1-53 1255 A₃ B-1-57 1256 A₃ B-1-61 1257 A₃ B-1-65 1258 A₃ B-1-69 1259 A₃ B-2-1 1260 A₃ B-2-9 1261 A₃ B-2-17 1262 A₃ B-2-25 1263 A₃ B-2-33 1264 A₃ B-2-41 1265 A₃ B-2-49 1266 A₃ B-2-57 1267 A₃ B-2-65 1268 A₃ B-2-73 1269 A₃ B-2-81 1270 A₃ B-2-89 1271 A₃ B-2-97 1272 A₃ B-2-105 1273 A₃ B-2-113 1274 A₃ B-2-121 1275 A₃ B-2-129 1276 A₃ B-2-137 1277 A₃ B-2-145 1278 A₃ B-2-146 1279 A₃ B-2-147 1280 A₃ B-2-148 1281 A₃ B-2-149 1282 A₃ B-2-150 1283 A₃ B-2-151 1284 A₃ B-2-152 1285 A₃ B-2-153 1286 A₃ B-2-154 1287 A₃ B-2-155 1288 A₃ B-2-156 1289 A₃ B-2-157 1290 A₃ B-2-158 1291 A₃ B-2-159 1292 A₃ B-2-160 1293 A₃ B-2-161 1294 A₃ B-2-162 1295 A₃ B-2-163 1296 A₃ B-2-164 1297 A₃ B-2-165 1298 A₃ B-2-166 1299 A₃ B-2-167 1300 A₃ B-2-168 1301 A₃ B-3-1 1302 A₃ B-3-9 1303 A₃ B-3-17 1304 A₃ B-3-25 1305 A₃ B-3-33 1306 A₃ B-3-41 1307 A₃ B-3-49 1308 A₃ B-3-57 1309 A₃ B-3-65 1310 A₃ B-3-73 1311 A₃ B-3-81 1312 A₃ B-3-89 1313 A₃ B-3-97 1314 A₃ B-3-105 1315 A₃ B-3-113 1316 A₃ B-3-121 1317 A₃ B-3-129 1318 A₃ B-3-145 1319 A₃ B-3-146 1320 A₃ B-3-147 1321 A₃ B-3-148 1322 A₃ B-3-149 1323 A₃ B-3-150 1324 A₃ B-3-151 1325 A₃ B-3-152 1326 A₃ B-3-153 1327 A₃ B-3-154 1328 A₃ B-3-155 1329 A₃ B-3-156 1330 A₃ B-3-157 1331 A₃ B-3-158 1332 A₃ B-3-159 1333 A₃ B-3-160 1334 A₃ B-3-161 1335 A₃ B-3-162 1336 A₃ B-3-163 1337 A₃ B-3-164 1338 A₃ B-3-165 1339 A₃ B-3-166 1340 A₃ B-3-167 1341 A₃ B-3-168 1342 A₃ B-3-137 1343 A₃ B-4-1 1344 A₃ B-4-5 1345 A₃ B-4-9 1346 A₃ B-4-13 1347 A₃ B-4-17 1348 A₃ B-4-21 1349 A₃ B-4-25 1350 A₃ B-4-29 1351 A₃ B-4-33 1352 A₃ B-4-37 1353 A₃ B-4-41 1354 A₃ B-4-45 1355 A₃ B-4-49 1356 A₃ B-4-53 1357 A₃ B-4-57 1358 A₃ B-4-61 1359 A₃ B-4-65 1360 A₃ B-4-69 1361 A₃ B-5-1 1362 A₃ B-5-5 1363 A₃ B-5-9 1364 A₃ B-5-13 1365 A₃ B-5-17 1366 A₃ B-5-21 1367 A₃ B-5-25 1368 A₃ B-5-29 1369 A₃ B-5-33 1370 A₃ B-5-37 1371 A₃ B-5-41 1372 A₃ B-5-45 1373 A₃ B-5-49 1374 A₃ B-5-53 1375 A₃ B-5-57 1376 A₃ B-5-61 1377 A₃ B-5-65 1378 A₃ B-5-69 1379 A₃ B-6-1 1380 A₃ B-6-2 1381 A₃ B-6-3 1382 A₃ B-6-4 1383 A₃ B-6-5 1384 A₃ B-6-6 1385 A₃ B-6-7 1386 A₃ B-6-8 1387 A₃ B-6-9 1388 A₃ B-6-10 1389 A₃ B-6-11 1390 A₃ B-6-12 1391 A₃ B-6-13 1392 A₃ B-6-14 1393 A₃ B-6-15 1394 A₃ B-6-16 1395 A₃ B-6-17 1396 A₃ B-6-18 1397 A₄ B-1-1 1398 A₄ B-1-5 1399 A₄ B-1-9 1400 A₄ B-1-13 1401 A₄ B-1-17 1402 A₄ B-1-21 1403 A₄ B-1-25 1404 A₄ B-1-29 1405 A₄ B-1-33 1406 A₄ B-1-37 1407 A₄ B-1-41 1408 A₄ B-1-45 1409 A₄ B-1-49 1410 A₄ B-1-53 1411 A₄ B-1-57 1412 A₄ B-1-61 1413 A₄ B-1-65 1414 A₄ B-1-69 1415 A₄ B-2-1 1416 A₄ B-2-9 1417 A₄ B-2-17 1418 A₄ B-2-25 1419 A₄ B-2-33 1420 A₄ B-2-41 1421 A₄ B-2-49 1422 A₄ B-2-57 1423 A₄ B-2-65 1424 A₄ B-2-73 1425 A₄ B-2-81 1426 A₄ B-2-89 1427 A₄ B-2-97 1428 A₄ B-2-105 1429 A₄ B-2-113 1430 A₄ B-2-121 1431 A₄ B-2-129 1432 A₄ B-2-137 1433 A₄ B-2-145 1434 A₄ B-2-146 1435 A₄ B-2-147 1436 A₄ B-2-148 1437 A₄ B-2-149 1438 A₄ B-2-150 1439 A₄ B-2-151 1440 A₄ B-2-152 1441 A₄ B-2-153 1442 A₄ B-2-154 1443 A₄ B-2-155 1444 A₄ B-2-156 1445 A₄ B-2-157 1446 A₄ B-2-158 1447 A₄ B-2-159 1448 A₄ B-2-160 1449 A₄ B-2-161 1450 A₄ B-2-162 1451 A₄ B-2-163 1452 A₄ B-2-164 1453 A₄ B-2-165 1454 A₄ B-2-166 1455 A₄ B-2-167 1456 A₄ B-2-168 1457 A₄ B-3-1 1458 A₄ B-3-9 1459 A₄ B-3-17 1460 A₄ B-3-25 1461 A₄ B-3-33 1462 A₄ B-3-41 1463 A₄ B-3-49 1464 A₄ B-3-57 1465 A₄ B-3-65 1466 A₄ B-3-73 1467 A₄ B-3-81 1468 A₄ B-3-89 1469 A₄ B-3-97 1470 A₄ B-3-105 1471 A₄ B-3-113 1472 A₄ B-3-121 1473 A₄ B-3-129 1474 A₄ B-3-137 1475 A₄ B-3-145 1476 A₄ B-3-146 1477 A₄ B-3-147 1478 A₄ B-3-148 1479 A₄ B-3-149 1480 A₄ B-3-150 1481 A₄ B-3-151 1482 A₄ B-3-152 1483 A₄ B-3-153 1484 A₄ B-3-154 1485 A₄ B-3-155 1486 A₄ B-3-156 1487 A₄ B-3-157 1488 A₄ B-3-158 1489 A₄ B-3-159 1490 A₄ B-3-160 1491 A₄ B-3-161 1492 A₄ B-3-162 1493 A₄ B-3-163 1494 A₄ B-3-164 1495 A₄ B-3-165 1496 A₄ B-3-166 1497 A₄ B-3-167 1498 A₄ B-3-168 1499 A₄ B-4-1 1500 A₄ B-4-5 1501 A₄ B-4-9 1502 A₄ B-4-13 1503 A₄ B-4-17 1504 A₄ B-4-21 1505 A₄ B-4-25 1506 A₄ B-4-29 1507 A₄ B-4-33 1508 A₄ B-4-37 1509 A₄ B-4-41 1510 A₄ B-4-45 1511 A₄ B-4-49 1512 A₄ B-4-53 1513 A₄ B-4-57 1514 A₄ B-4-61 1515 A₄ B-4-65 1516 A₄ B-4-69 1517 A₄ B-5-1 1518 A₄ B-5-5 1519 A₄ B-5-9 1520 A₄ B-5-13 1521 A₄ B-5-17 1522 A₄ B-5-21 1523 A₄ B-5-25 1524 A₄ B-5-29 1525 A₄ B-5-33 1526 A₄ B-5-37 1527 A₄ B-5-41 1528 A₄ B-5-45 1529 A₄ B-5-49 1530 A₄ B-5-53 1531 A₄ B-5-57 1532 A₄ B-5-61 1533 A₄ B-5-65 1534 A₄ B-5-69 1535 A₄ B-6-1 1536 A₄ B-6-2 1537 A₄ B-6-3 1538 A₄ B-6-4 1539 A₄ B-6-5 1540 A₄ B-6-6 1541 A₄ B-6-7 1542 A₄ B-6-8 1543 A₄ B-6-9 1544 A₄ B-6-10 1545 A₄ B-6-11 1546 A₄ B-6-12 1547 A₄ B-6-13 1548 A₄ B-6-14 1549 A₄ B-6-15 1550 A₄ B-6-16 1551 A₄ B-6-17 1552 A₄ B-6-18 1553 A₅ B-1-1 1554 A₅ B-1-5 1555 A₅ B-1-9 1556 A₅ B-1-13 1557 A₅ B-1-17 1558 A₅ B-1-21 1559 A₅ B-1-25 1560 A₅ B-1-29 1561 A₅ B-1-33 1562 A₅ B-1-37 1563 A₅ B-1-41 1564 A₅ B-1-45 1565 A₅ B-1-49 1566 A₅ B-1-53 1567 A₅ B-1-57 1568 A₅ B-1-61 1569 A₅ B-1-65 1570 A₅ B-1-69 1571 A₅ B-2-1 1572 A₅ B-2-9 1573 A₅ B-2-17 1574 A₅ B-2-25 1575 A₅ B-2-33 1576 A₅ B-2-41 1577 A₅ B-2-49 1578 A₅ B-2-57 1579 A₅ B-2-65 1580 A₅ B-2-73 1581 A₅ B-2-81 1582 A₅ B-2-89 1583 A₅ B-2-97 1584 A₅ B-2-105 1585 A₅ B-2-113 1586 A₅ B-2-121 1587 A₅ B-2-129 1588 A₅ B-2-137 1589 A₅ B-2-145 1590 A₅ B-2-146 1591 A₅ B-2-147 1592 A₅ B-2-148 1593 A₅ B-2-149 1594 A₅ B-2-150 1595 A₅ B-2-151 1596 A₅ B-2-152 1597 A₅ B-2-153 1598 A₅ B-2-154 1599 A₅ B-2-155 1600 A₅ B-2-156 1601 A₅ B-2-157 1602 A₅ B-2-158 1603 A₅ B-2-159 1604 A₅ B-2-160 1605 A₅ B-2-161 1606 A₅ B-2-162 1607 A₅ B-2-163 1608 A₅ B-2-164 1609 A₅ B-2-165 1610 A₅ B-2-166 1611 A₅ B-2-167 1612 A₅ B-2-168 1613 A₅ B-3-1 1614 A₅ B-3-9 1615 A₅ B-3-17 1616 A₅ B-3-25 1617 A₅ B-3-33 1618 A₅ B-3-41 1619 A₅ B-3-49 1620 A₅ B-3-57 1621 A₅ B-3-65 1622 A₅ B-3-73 1623 A₅ B-3-81 1624 A₅ B-3-89 1625 A₅ B-3-97 1626 A₅ B-3-105 1627 A₅ B-3-113 1628 A₅ B-3-121 1629 A₅ B-3-129 1630 A₅ B-3-137 1631 A₅ B-3-145 1632 A₅ B-3-146 1633 A₅ B-3-147 1634 A₅ B-3-148 1635 A₅ B-3-149 1636 A₅ B-3-150 1637 A₅ B-3-151 1638 A₅ B-3-152 1639 A₅ B-3-153 1640 A₅ B-3-154 1641 A₅ B-3-155 1642 A₅ B-3-156 1643 A₅ B-3-157 1644 A₅ B-3-158 1645 A₅ B-3-159 1646 A₅ B-3-160 1647 A₅ B-3-161 1648 A₅ B-3-162 1649 A₅ B-3-163 1650 A₅ B-3-164 1651 A₅ B-3-165 1652 A₅ B-3-166 1653 A₅ B-3-167 1654 A₅ B-3-168 1655 A₅ B-4-1 1656 A₅ B-4-5 1657 A₅ B-4-9 1658 A₅ B-4-13 1659 A₅ B-4-17 1660 A₅ B-4-21 1661 A₅ B-4-25 1662 A₅ B-4-29 1663 A₅ B-4-33 1664 A₅ B-4-37 1665 A₅ B-4-41 1666 A₅ B-4-45 1667 A₅ B-4-49 1668 A₅ B-4-53 1669 A₅ B-4-57 1670 A₅ B-4-61 1671 A₅ B-4-65 1672 A₅ B-4-69 1673 A₅ B-5-1 1674 A₅ B-5-5 1675 A₅ B-5-9 1676 A₅ B-5-13 1677 A₅ B-5-17 1678 A₅ B-5-21 1679 A₅ B-5-25 1680 A₅ B-5-29 1681 A₅ B-5-33 1682 A₅ B-5-37 1683 A₅ B-5-41 1684 A₅ B-5-45 1685 A₅ B-5-49 1686 A₅ B-5-53 1687 A₅ B-5-57 1688 A₅ B-5-61 1689 A₅ B-5-65 1690 A₅ B-5-69 1691 A₅ B-6-1 1692 A₅ B-6-2 1693 A₅ B-6-3 1694 A₅ B-6-4 1695 A₅ B-6-5 1696 A₅ B-6-6 1697 A₅ B-6-7 1698 A₅ B-6-8 1699 A₅ B-6-9 1700 A₅ B-6-10 1701 A₅ B-6-11 1702 A₅ B-6-12 1703 A₅ B-6-13 1704 A₅ B-6-14 1705 A₅ B-6-15 1706 A₅ B-6-16 1707 A₅ B-6-17 1708 A₅ B-6-18 1709 A₆ B-1-1 1710 A₆ B-1-5 1711 A₆ B-1-9 1712 A₆ B-1-13 1713 A₆ B-1-17 1714 A₆ B-1-21 1715 A₆ B-1-25 1716 A₆ B-1-29 1717 A₆ B-1-33 1718 A₆ B-1-37 1719 A₆ B-1-41 1720 A₆ B-1-45 1721 A₆ B-1-49 1722 A₆ B-1-53 1723 A₆ B-1-57 1724 A₆ B-1-61 1725 A₆ B-1-65 1726 A₆ B-1-69 1727 A₆ B-2-1 1728 A₆ B-2-9 1729 A₆ B-2-17 1730 A₆ B-2-25 1731 A₆ B-2-33 1732 A₆ B-2-41 1733 A₆ B-2-49 1734 A₆ B-2-57 1735 A₆ B-2-65 1736 A₆ B-2-73 1737 A₆ B-2-81 1738 A₆ B-2-89 1739 A₆ B-2-97 1740 A₆ B-2-105 1741 A₆ B-2-113 1742 A₆ B-2-121 1743 A₆ B-2-129 1744 A₆ B-2-137 1745 A₆ B-2-145 1746 A₆ B-2-146 1747 A₆ B-2-147 1748 A₆ B-2-148 1749 A₆ B-2-149 1750 A₆ B-2-150 1751 A₆ B-2-151 1752 A₆ B-2-152 1753 A₆ B-2-153 1754 A₆ B-2-154 1755 A₆ B-2-155 1756 A₆ B-2-156 1757 A₆ B-2-157 1758 A₆ B-2-158 1759 A₆ B-2-159 1760 A₆ B-2-160 1761 A₆ B-2-161 1762 A₆ B-2-162 1763 A₆ B-2-163 1764 A₆ B-2-164 1765 A₆ B-2-165 1766 A₆ B-2-166 1767 A₆ B-2-167 1768 A₆ B-2-168 1769 A₆ B-3-1 1770 A₆ B-3-9 1771 A₆ B-3-17 1772 A₆ B-3-25 1773 A₆ B-3-33 1774 A₆ B-3-41 1775 A₆ B-3-49 1776 A₆ B-3-57 1777 A₆ B-3-65 1778 A₆ B-3-73 1779 A₆ B-3-81 1780 A₆ B-3-89 1781 A₆ B-3-97 1782 A₆ B-3-105 1783 A₆ B-3-113 1784 A₆ B-3-121 1785 A₆ B-3-129 1786 A₆ B-3-137 1787 A₆ B-3-145 1788 A₆ B-3-146 1789 A₆ B-3-147 1790 A₆ B-3-148 1791 A₆ B-3-149 1792 A₆ B-3-150 1793 A₆ B-3-151 1794 A₆ B-3-152 1795 A₆ B-3-153 1796 A₆ B-3-154 1797 A₆ B-3-155 1798 A₆ B-3-156 1799 A₆ B-3-157 1800 A₆ B-3-158 1801 A₆ B-3-159 1802 A₆ B-3-160 1803 A₆ B-3-161 1804 A₆ B-3-162 1805 A₆ B-3-163 1806 A₆ B-3-164 1807 A₆ B-3-165 1808 A₆ B-3-166 1809 A₆ B-3-167 1810 A₆ B-3-168 1811 A₆ B-4-1 1812 A₆ B-4-5 1813 A₆ B-4-9 1814 A₆ B-4-13 1815 A₆ B-4-17 1816 A₆ B-4-21 1817 A₆ B-4-25 1818 A₆ B-4-29 1819 A₆ B-4-33 1820 A₆ B-4-37 1821 A₆ B-4-41 1822 A₆ B-4-45 1823 A₆ B-4-49 1824 A₆ B-4-53 1825 A₆ B-4-57 1826 A₆ B-4-61 1827 A₆ B-4-65 1828 A₆ B-4-69 1829 A₆ B-5-1 1830 A₆ B-5-5 1831 A₆ B-5-9 1832 A₆ B-5-13 1833 A₆ B-5-17 1834 A₆ B-5-21 1835 A₆ B-5-25 1836 A₆ B-5-29 1837 A₆ B-5-33 1838 A₆ B-5-37 1839 A₆ B-5-41 1840 A₆ B-5-45 1841 A₆ B-5-49 1842 A₆ B-5-53 1843 A₆ B-5-57 1844 A₆ B-5-61 1845 A₆ B-5-65 1846 A₆ B-5-69 1847 A₆ B-6-1 1848 A₆ B-6-2 1849 A₆ B-6-3 1850 A₆ B-6-4 1851 A₆ B-6-5 1852 A₆ B-6-6 1853 A₆ B-6-7 1854 A₆ B-6-8 1855 A₆ B-6-9 1856 A₆ B-6-10 1857 A₆ B-6-11 1858 A₆ B-6-12 1859 A₆ B-6-13 1860 A₆ B-6-14 1861 A₆ B-6-15 1862 A₆ B-6-16 1863 A₆ B-6-17 1864 A₆ B-6-18 1865 A₇ B-1-1 1866 A₇ B-1-5 1867 A₇ B-1-9 1868 A₇ B-1-13 1869 A₇ B-1-17 1870 A₇ B-1-21 1871 A₇ B-1-25 1872 A₇ B-1-29 1873 A₇ B-1-33 1874 A₇ B-1-37 1875 A₇ B-1-41 1876 A₇ B-1-45 1877 A₇ B-1-49 1878 A₇ B-1-53 1879 A₇ B-1-57 1880 A₇ B-1-61 1881 A₇ B-1-65 1882 A₇ B-1-69 1883 A₇ B-2-1 1884 A₇ B-2-9 1885 A₇ B-2-17 1886 A₇ B-2-25 1887 A₇ B-2-33 1888 A₇ B-2-41 1889 A₇ B-2-49 1890 A₇ B-2-57 1891 A₇ B-2-65 1892 A₇ B-2-73 1893 A₇ B-2-81 1894 A₇ B-2-89 1895 A₇ B-2-97 1896 A₇ B-2-105 1897 A₇ B-2-113 1898 A₇ B-2-121 1899 A₇ B-2-129 1900 A₇ B-2-137 1901 A₇ B-2-145 1902 A₇ B-2-146 1903 A₇ B-2-147 1904 A₇ B-2-148 1905 A₇ B-2-149 1906 A₇ B-2-150 1907 A₇ B-2-151 1908 A₇ B-2-152 1909 A₇ B-2-153 1910 A₇ B-2-154 1911 A₇ B-2-155 1912 A₇ B-2-156 1913 A₇ B-2-157 1914 A₇ B-2-158 1915 A₇ B-2-159 1916 A₇ B-2-160 1917 A₇ B-2-161 1918 A₇ B-2-162 1919 A₇ B-2-163 1920 A₇ B-2-164 1921 A₇ B-2-165 1922 A₇ B-2-166 1923 A₇ B-2-167 1924 A₇ B-2-168 1925 A₇ B-3-1 1926 A₇ B-3-9 1927 A₇ B-3-17 1928 A₇ B-3-25 1929 A₇ B-3-33 1930 A₇ B-3-41 1931 A₇ B-3-49 1932 A₇ B-3-57 1933 A₇ B-3-65 1934 A₇ B-3-73 1935 A₇ B-3-81 1936 A₇ B-3-89 1937 A₇ B-3-97 1938 A₇ B-3-105 1939 A₇ B-3-113 1940 A₇ B-3-121 1941 A₇ B-3-129 1942 A₇ B-3-137 1943 A₇ B-3-145 1944 A₇ B-3-146 1945 A₇ B-3-147 1946 A₇ B-3-148 1947 A₇ B-3-149 1948 A₇ B-3-150 1949 A₇ B-3-151 1950 A₇ B-3-152 1951 A₇ B-3-153 1952 A₇ B-3-154 1953 A₇ B-3-155 1954 A₇ B-3-156 1955 A₇ B-3-157 1956 A₇ B-3-158 1957 A₇ B-3-159 1958 A₇ B-3-160 1959 A₇ B-3-161 1960 A₇ B-3-162 1961 A₇ B-3-163 1962 A₇ B-3-164 1963 A₇ B-3-165 1964 A₇ B-3-166 1965 A₇ B-3-167 1966 A₇ B-3-168 1967 A₇ B-4-1 1968 A₇ B-4-5 1969 A₇ B-4-9 1970 A₇ B-4-13 1971 A₇ B-4-17 1972 A₇ B-4-21 1973 A₇ B-4-25 1974 A₇ B-4-29 1975 A₇ B-4-33 1976 A₇ B-4-37 1977 A₇ B-4-41 1978 A₇ B-4-45 1979 A₇ B-4-49 1980 A₇ B-4-53 1981 A₇ B-4-57 1982 A₇ B-4-61 1983 A₇ B-4-65 1984 A₇ B-4-69 1985 A₇ B-5-1 1986 A₇ B-5-5 1987 A₇ B-5-9 1988 A₇ B-5-13 1989 A₇ B-5-17 1990 A₇ B-5-21 1991 A₇ B-5-25 1992 A₇ B-5-29 1993 A₇ B-5-33 1994 A₇ B-5-37 1995 A₇ B-5-41 1996 A₇ B-5-45 1997 A₇ B-5-49 1998 A₇ B-5-53 1999 A₇ B-5-57 2000 A₇ B-5-61 2001 A₇ B-5-65 2002 A₇ B-5-69 2003 A₇ B-6-1 2004 A₇ B-6-2 2005 A₇ B-6-3 2006 A₇ B-6-4 2007 A₇ B-6-5 2008 A₇ B-6-6 2009 A₇ B-6-7 2010 A₇ B-6-8 2011 A₇ B-6-9 2012 A₇ B-6-10 2013 A₇ B-6-11 2014 A₇ B-6-12 2015 A₇ B-6-13 2016 A₇ B-6-14 2017 A₇ B-6-15 2018 A₇ B-6-16 2019 A₇ B-6-17 2020 A₇ B-6-18 2021 A₈ B-1-1 2022 A₈ B-1-5 2023 A₈ B-1-9 2024 A₈ B-1-13 2025 A₈ B-1-17 2026 A₈ B-1-21 2027 A₈ B-1-25 2028 A₈ B-1-29 2029 A₈ B-1-33 2030 A₈ B-1-37 2031 A₈ B-1-41 2032 A₈ B-1-45 2033 A₈ B-1-49 2034 A₈ B-1-53 2035 A₈ B-1-57 2036 A₈ B-1-61 2037 A₈ B-1-65 2038 A₈ B-1-69 2039 A₈ B-2-1 2040 A₈ B-2-9 2041 A₈ B-2-17 2042 A₈ B-2-25 2043 A₈ B-2-33 2044 A₈ B-2-41 2045 A₈ B-2-49 2046 A₈ B-2-57 2047 A₈ B-2-65 2048 A₈ B-2-73 2049 A₈ B-2-81 2050 A₈ B-2-89 2051 A₈ B-2-97 2052 A₈ B-2-105 2053 A₈ B-2-113 2054 A₈ B-2-121 2055 A₈ B-2-129 2056 A₈ B-2-137 2057 A₈ B-2-145 2058 A₈ B-2-146 2059 A₈ B-2-147 2060 A₈ B-2-148 2061 A₈ B-2-149 2062 A₈ B-2-150 2063 A₈ B-2-151 2064 A₈ B-2-152 2065 A₈ B-2-153 2066 A₈ B-2-154 2067 A₈ B-2-155 2068 A₈ B-2-156 2069 A₈ B-2-157 2070 A₈ B-2-158 2071 A₈ B-2-159 2072 A₈ B-2-160 2073 A₈ B-2-161 2074 A₈ B-2-162 2075 A₈ B-2-163 2076 A₈ B-2-164 2077 A₈ B-2-165 2078 A₈ B-2-166 2079 A₈ B-2-167 2080 A₈ B-2-168 2081 A₈ B-3-1 2082 A₈ B-3-9 2083 A₈ B-3-17 2084 A₈ B-3-25 2085 A₈ B-3-33 2086 A₈ B-3-41 2087 A₈ B-3-49 2088 A₈ B-3-57 2089 A₈ B-3-65 2090 A₈ B-3-73 2091 A₈ B-3-81 2092 A₈ B-3-89 2093 A₈ B-3-97 2094 A₈ B-3-105 2095 A₈ B-3-113 2096 A₈ B-3-121 2097 A₈ B-3-129 2098 A₈ B-3-137 2099 A₈ B-3-145 2100 A₈ B-3-146 2101 A₈ B-3-147 2102 A₈ B-3-148 2103 A₈ B-3-149 2104 A₈ B-3-150 2105 A₈ B-3-151 2106 A₈ B-3-152 2107 A₈ B-3-153 2108 A₈ B-3-154 2109 A₈ B-3-155 2110 A₈ B-3-156 2111 A₈ B-3-157 2112 A₈ B-3-158 2113 A₈ B-3-159 2114 A₈ B-3-160 2115 A₈ B-3-161 2116 A₈ B-3-162 2117 A₈ B-3-163 2118 A₈ B-3-164 2119 A₈ B-3-165 2120 A₈ B-3-166 2121 A₈ B-3-167 2122 A₈ B-3-168 2123 A₈ B-4-1 2124 A₈ B-4-5 2125 A₈ B-4-9 2126 A₈ B-4-13 2127 A₈ B-4-17 2128 A₈ B-4-21 2129 A₈ B-4-25 2130 A₈ B-4-29 2131 A₈ B-4-33 2132 A₈ B-4-37 2133 A₈ B-4-41 2134 A₈ B-4-45 2135 A₈ B-4-49 2136 A₈ B-4-53 2137 A₈ B-4-57 2138 A₈ B-4-61 2139 A₈ B-4-65 2140 A₈ B-4-69 2141 A₈ B-5-1 2142 A₈ B-5-5 2143 A₈ B-5-9 2144 A₈ B-5-13 2145 A₈ B-5-17 2146 A₈ B-5-21 2147 A₈ B-5-25 2148 A₈ B-5-29 2149 A₈ B-5-33 2150 A₈ B-5-37 2151 A₈ B-5-41 2152 A₈ B-5-45 2153 A₈ B-5-49 2154 A₈ B-5-53 2155 A₈ B-5-57 2156 A₈ B-5-61 2157 A₈ B-5-65 2158 A₈ B-5-69 2159 A₈ B-6-1 2160 A₈ B-6-2 2161 A₈ B-6-3 2162 A₈ B-6-4 2163 A₈ B-6-5 2164 A₈ B-6-6 2165 A₈ B-6-7 2166 A₈ B-6-8 2167 A₈ B-6-9 2168 A₈ B-6-10 2169 A₈ B-6-11 2170 A₈ B-6-12 2171 A₈ B-6-13 2172 A₈ B-6-14 2173 A₈ B-6-15 2174 A₈ B-6-16 2175 A₈ B-6-17 2176 A₈ B-6-18 2177 A₉ B-1-1 2178 A₉ B-1-5 2179 A₉ B-1-9 2180 A₉ B-1-13 2181 A₉ B-1-17 2182 A₉ B-1-21 2183 A₉ B-1-25 2184 A₉ B-1-29 2185 A₉ B-1-33 2186 A₉ B-1-37 2187 A₉ B-1-41 2188 A₉ B-1-45 2189 A₉ B-1-49 2190 A₉ B-1-53 2191 A₉ B-1-57 2192 A₉ B-1-61 2193 A₉ B-1-65 2194 A₉ B-1-69 2195 A₉ B-2-1 2196 A₉ B-2-9 2197 A₉ B-2-17 2198 A₉ B-2-25 2199 A₉ B-2-33 2200 A₉ B-2-41 2201 A₉ B-2-49 2202 A₉ B-2-57 2203 A₉ B-2-65 2204 A₉ B-2-73 2205 A₉ B-2-81 2206 A₉ B-2-89 2207 A₉ B-2-97 2208 A₉ B-2-105 2209 A₉ B-2-113 2210 A₉ B-2-121 2211 A₉ B-2-129 2212 A₉ B-2-137 2213 A₉ B-2-145 2214 A₉ B-2-146 2215 A₉ B-2-147 2216 A₉ B-2-148 2217 A₉ B-2-149 2218 A₉ B-2-150 2219 A₉ B-2-151 2220 A₉ B-2-152 2221 A₉ B-2-153 2222 A₉ B-2-154 2223 A₉ B-2-155 2224 A₉ B-2-156 2225 A₉ B-2-157 2226 A₉ B-2-158 2227 A₉ B-2-159 2228 A₉ B-2-160 2229 A₉ B-2-161 2230 A₉ B-2-162 2231 A₉ B-2-163 2232 A₉ B-2-164 2233 A₉ B-2-165 2234 A₉ B-2-166 2235 A₉ B-2-167 2236 A₉ B-2-168 2237 A₉ B-3-1 2238 A₉ B-3-9 2239 A₉ B-3-17 2240 A₉ B-3-25 2241 A₉ B-3-33 2242 A₉ B-3-41 2243 A₉ B-3-49 2244 A₉ B-3-57 2245 A₉ B-3-65 2246 A₉ B-3-73 2247 A₉ B-3-81 2248 A₉ B-3-89 2249 A₉ B-3-97 2250 A₉ B-3-105 2251 A₉ B-3-113 2252 A₉ B-3-121 2253 A₉ B-3-129 2254 A₉ B-3-137 2255 A₉ B-3-145 2256 A₉ B-3-146 2257 A₉ B-3-147 2258 A₉ B-3-148 2259 A₉ B-3-149 2260 A₉ B-3-150 2261 A₉ B-3-151 2262 A₉ B-3-152 2263 A₉ B-3-153 2264 A₉ B-3-154 2265 A₉ B-3-155 2266 A₉ B-3-156 2267 A₉ B-3-157 2268 A₉ B-3-158 2269 A₉ B-3-159 2270 A₉ B-3-160 2271 A₉ B-3-161 2272 A₉ B-3-162 2273 A₉ B-3-163 2274 A₉ B-3-164 2275 A₉ B-3-165 2276 A₉ B-3-166 2277 A₉ B-3-167 2278 A₉ B-3-168 2279 A₉ B-4-1 2280 A₉ B-4-5 2281 A₉ B-4-9 2282 A₉ B-4-13 2283 A₉ B-4-17 2284 A₉ B-4-21 2285 A₉ B-4-25 2286 A₉ B-4-29 2287 A₉ B-4-33 2288 A₉ B-4-37 2289 A₉ B-4-41 2290 A₉ B-4-45 2291 A₉ B-4-49 2292 A₉ B-4-53 2293 A₉ B-4-57 2294 A₉ B-4-61 2295 A₉ B-4-65 2296 A₉ B-4-69 2297 A₉ B-5-1 2298 A₉ B-5-5 2299 A₉ B-5-9 2300 A₉ B-5-13 2301 A₉ B-5-17 2302 A₉ B-5-21 2303 A₉ B-5-25 2304 A₉ B-5-29 2305 A₉ B-5-33 2306 A₉ B-5-37 2307 A₉ B-5-41 2308 A₉ B-5-45 2309 A₉ B-5-49 2310 A₉ B-5-53 2311 A₉ B-5-57 2312 A₉ B-5-61 2313 A₉ B-5-65 2314 A₉ B-5-69 2315 A₉ B-6-1 2316 A₉ B-6-2 2317 A₉ B-6-3 2318 A₉ B-6-4 2319 A₉ B-6-5 2320 A₉ B-6-6 2321 A₉ B-6-7 2322 A₉ B-6-8 2323 A₉ B-6-9 2324 A₉ B-6-10 2325 A₉ B-6-11 2326 A₉ B-6-12 2327 A₉ B-6-13 2328 A₉ B-6-14 2329 A₉ B-6-15 2330 A₉ B-6-16 2331 A₉ B-6-17 2332 A₉ B-6-18 2333 A₁ B-3-219 2334 A₁ B-3-220 2335 A₁ B-3-221 2336 A₁ B-3-222 2337 A₁ B-3-223 2338 A₁ B-3-224 2339 A₁ B-3-225 2340 A₁ B-3-226 2341 A₁ B-3-227 2342 A₁ B-3-228 2343 A₁ B-3-229 2344 A₁ B-3-230 2345 A₁ B-3-231 2346 A₁ B-3-232 2347 A₁ B-3-233 2348 A₁ B-3-234 2349 A₁ B-3-235 2350 A₁₀ B-3-57 2351 A₁₀ B-3-58 2352 A₁₀ B-3-59 2353 A₁₀ B-3-60 2354 A₁₀ B-3-61 2355 A₁₀ B-3-62 2356 A₁₀ B-3-63 2357 A₁₀ B-3-64 2358 A₁₀ B-3-65 2359 A₁₀ B-3-66 2360 A₁₀ B-3-67 2361 A₁₀ B-3-68 2362 A₁₀ B-3-69 2363 A₁₀ B-3-70 2364 A₁₀ B-3-71 2365 A₁₀ B-3-72 2366 A₁₀ B-3-129 2367 A₁₀ B-3-130 2368 A₁₀ B-3-131 2369 A₁₀ B-3-132 2370 A₁₀ B-3-133 2371 A₁₀ B-3-134 2372 A₁₀ B-3-135 2373 A₁₀ B-3-136 2374 A₁₀ B-3-137 2375 A₁₀ B-3-138 2376 A₁₀ B-3-139 2377 A₁₀ B-3-140 2378 A₁₀ B-3-141 2379 A₁₀ B-3-142 2380 A₁₀ B-3-143 2381 A₁₀ B-3-144 2382 A₁₀ B-3-219 2383 A₁₀ B-3-220 2384 A₁₀ B-3-221 2385 A₁₀ B-3-222 2386 A₁₀ B-3-223 2387 A₁₀ B-3-224 2388 A₁₀ B-3-225 2389 A₁₀ B-3-226 2390 A₁₀ B-3-227 2391 A₁₀ B-3-228 2392 A₁₀ B-3-229 2393 A₁₀ B-3-230 2394 A₁₀ B-3-231 2395 A₁₀ B-3-232 2396 A₁₀ B-3-233 2397 A₁₀ B-3-234 2398 A₁₀ B-3-235

wherein A₁ to A₁₀ in the above table have the following structures:

wherein in the structures of A₁ to A₁₀, * represents a position where B is joined.
 17. The compound of claim 16, wherein hydrogen in the compounds 1 to 2398 may be partially or fully deuterated.
 18. An electroluminescent device, comprising: an anode, a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises the compound of claim
 1. 19. The electroluminescent device of claim 18, wherein the organic layer is a light-emitting layer, and the compound is a light-emitting material; preferably, wherein the light-emitting layer further comprises a compound represented by Formula 16:

wherein R_(g1) to R_(g8) are each independently selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a thiol group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof; and wherein R_(g9) to R_(g10) are each independently selected from substituted or unsubstituted aryl having 6 to 30 carbon atoms or substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms.
 20. A compound formulation, comprising the compound of claim
 1. 